Microbiocidal 2-acylamino-thiazole-4-carboxamide derivatives

ABSTRACT

Compounds of the formula (I) wherein the substituents are as defined in claim 1, useful as pesticides, and especially fungicides.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a 371 National Stage application of InternationalApplication No. PCT/EP2019/082978 filed Nov. 28, 2019, claims priorityto EP 18209586.9 filed Nov. 30, 2018, the entire contents of theseapplications are hereby incorporated by reference.

The present invention relates to microbiocidal thiazole derivatives,e.g., as active ingredients, which have microbiocidal activity, inparticular fungicidal activity. The invention also relates to thepreparation of these thiazole derivatives, to agrochemical compositionswhich comprise at least one of the thiazole derivatives and to uses ofthe thiazole derivatives or compositions thereof in agriculture orhorticulture for controlling or preventing the infestation of plants,harvested food crops, seeds or non-living materials by phytopathogenicmicroorganisms, preferably fungi.

WO 2010/012793 and WO 2017/207362 describe thiazole derivatives aspesticidal agents.

According to the present invention, there is provided a compound offormula (I):

wherein

Y is C—F, C—H or N;

R¹ is hydrogen, C₁-C₆alkyl, C₁-C₆alkoxy, C₁-C₆haloalkyl,C₁-C₆hydroxyalkyl, C₁-C₆alkoxyC₁-C₆alkyl, C₃-C₆cycloalkyl,C₁-C₆alkoxyC₁-C₃alkoxy, C₁-C₆alkoxycarbonyl,C₁-C₆alkoxycarbonylC₁-C₃alkyl, C₁-C₆alkoxycarbonyloxyC₁-C₄alkyl,C₁-C₆alkycarbonyloxyC₁-C₄alkyl, C₂-C₆alkenyloxy, C₂ ⁻ C₆alkynyloxy,C₁-C₆alkylsulfanyl, di(C₁-C₆alkyl)amino, phenyl, phenylC₁-C₃alkyl,phenylC₁-C₃alkoxyC₁-C₃alkyl, phenoxy, or heteroaryl wherein theheteroaryl is a 5- or 6-membered aromatic monocyclic ring comprising 1or 2 heteroatoms individually selected from nitrogen, oxygen and sulfur;

R² is hydrogen, halogen, cyano, C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄aloalkyl,or HC(O)NH—;

R³ is C₁-C₈alkyl, C₁-C₈haloalkyl, C₁-C₈alkoxy, C₃-C₈cycloalkyl,C₃-C₈cycloalkylC₁-C₂alkyl (wherein the cycloalkyl groups are optionallysubstituted with 1 to 3 groups represented by R⁴), phenyl,phenylC₁-C₂alkyl, heteroaryl, heteroarylC₁-C₂alkyl, wherein theheteroaryl is a 5- or 6-membered aromatic monocyclic ring comprising 1,2, 3 or 4 heteroatoms individually selected from nitrogen, oxygen andsulfur, heterocyclyl, heterocyclylC₁-C₂alkyl, wherein the heterocyclylis a 4-, 5- or 6-membered non-aromatic monocyclic ring comprising 1, 2or 3 heteroatoms individually selected from nitrogen, oxygen and sulfur,or a 5- to 10-membered non-aromatic spirocyclic carbobi- orcarbotri-cyclyl ring system optionally comprising 1, 2, 3, 4 orheteroatoms individually selected from nitrogen, oxygen and sulfur, andwherein said spirocyclic carbobi- or carbotri-cyclyl ring systems areeach optionally bonded to the rest of the molecule through aC₁-C₂alkylene linker;

R⁴ is halogen, C₁-C₄alkyl, C₁-C₄alkoxy, or C₁-C₄haloalkyl;

X is N or C—H;

or a salt or an N-oxide thereof.

Wherein the compound of formula (I) is not2-(N-acetyl-3-fluoro-anilino)-N-isopropyl-5-methyl-thiazole-4-carboxamideor2-(N-acetyl-3-fluoro-anilino)-5-methyl-N-sec-butyl-thiazole-4-carboxamide.

Surprisingly, it has been found that the novel compounds of formula (I)have, for practical purposes, a very advantageous level of biologicalactivity for protecting plants against diseases that are caused byfungi.

Further to this, it has been found that that the novel compounds offormula (I) wherein R¹ is hydrogen, C₁-C₆alkyl, C₁-C₆alkoxy,C₁-C₆haloalkyl, C₁-C₆hydroxyalkyl,C₁-C₆alkoxyC₁-C₆alkyl,C₃-C₆cycloalkyl, C₁-C₆alkoxyC₁-C₃alkoxy, C₁-C₆alkoxycarbonyl,C₁-C₆alkoxycarbonylC₁-C₄alkyl, C₁-C₆alkoxycarbonyloxyC₁-C₄alkyl,C₁-C₆alkycarbonyloxyC₁-C₄alkyl, C₂-C₆alkenyloxy, C₂-C₆alkynyloxy,C₁-C₆alkylsulfanyl, di(C₁-C₆alkyl)amino, phenyl, phenylC₁-C₃alkyl,phenylC₁-C₃alkoxyC₁-C₃alkyl, phenoxy, or heteroaryl, wherein theheteroaryl is a 5- or 6-membered aromatic monocyclic ring comprising 1or 2 heteroatoms individually selected from nitrogen, oxygen and sulfur,in particular when R¹ is hydrogen, C₁-C₆alkyl, C₁-C₆alkoxy,C₁-C₆haloalkyl, C₁-C₆alkoxyC₁-C₆alkyl, C₃-C₆cycloalkyl,C₁-C₆alkoxyC₁-C₃alkoxy, C₁-C₆alkoxycarbonyl,C₁-C₆alkoxycarbonylC₁-C₄alkyl, C₂-C₆alkenyloxy, C₂- C₆alkynyloxy,C₁-C₆alkylsulfanyl, phenyl, phenoxy, or heteroaryl, wherein theheteroaryl is a 5- or 6-25 membered aromatic monocyclic ring comprising1 or 2 heteroatoms individually selected from nitrogen, oxygen andsulfur, may show improved solubility properties (in particular innon-polar solvents), and/or photostability properties when compared totheir corresponding free amine, which are known for example from WO2017/207362.

According to a second aspect of the invention, there is provided anagrochemical composition comprising a fungicidally effective amount of acompound of formula (I) according to the present invention. Such anagricultural composition may further comprise at least one additionalactive ingredient and/or an agrochemically-acceptable diluent orcarrier.

According to a third aspect of the invention, there is provided a methodof controlling or preventing infestation of useful plants byphytopathogenic microorganisms, wherein a fungicidally effective amountof a compound of formula (I), ora composition comprising this compoundas active ingredient, is applied to the plants, to parts thereof or thelocus thereof.

According to a fourth aspect of the invention, there is provided the useof a compound of formula (I) as a fungicide. According to thisparticular aspect of the invention, the use may or may not includemethods for the treatment of the human or animal body by surgery ortherapy.

Where substituents are indicated as being “optionally substituted”, thismeans that they may or may not carry one or more identical or differentsubstituents, e.g., one, two or three R⁴substituents. For example,C₁-C₈alkyl substituted by 1, 2 or 3 halogens, may include, but not belimited to, —CH₂Cl, —CHCl₂, —CCl₃, —CH₂F, —CHF₂, —CF₃, —CH₂CF₃ or—CF₂CH₃ groups. As another example, C₁-C₆alkoxy substituted by 1, 2 or 3halogens, may include, but not limited to, CH₂ClO—, CHCl₂O—, CCl₃O—,CH₂FO—, CHF₂O—, CF₃O—, CF₃CH₂O— or CH₃CF₂O— groups.

As used herein, the term “cyano” means a —CN group. As used herein, theterm “halogen” refers to fluorine (fluoro), chlorine (chloro), bromine(bromo) or iodine (iodo).

As used herein, the term “Cl₁-C₈alkyl” refers to a straight or branchedhydrocarbon chain radical consisting solely of carbon and hydrogenatoms, containing no unsaturation, having from one to eight carbonatoms, and which is attached to the rest of the molecule by a singlebond. “C₁-C₆alkyl”, “C₁-C₄alkyl” and “C₁-C₃alkyl” are to be construedaccordingly. Examples of C₁-C₈alkyl include, but are not limited to,methyl, ethyl, n-propyl, and the isomers thereof, for example,iso-propyl. A “C₁-C₆alkylene” group refers to the correspondingdefinition of C₁-C₆alkyl, except that such radical is attached to therest of the molecule by two single bonds. The term “C₁-C₂alkylene” is tobe construed accordingly. Examples of C₁-C₆alkylene, include, but arenot limited to, —CH₂—, —CH₂CH₂— and —(CH₂)₃—.

As used herein, the term “C₁-C₆hydroxyalkyl” refers a C₁-C₈alkyl radicalas generally defined above substituted by one or more hydroxy groups.Examples of C₁-C₆hydroxyalkyl include but are not limited to1-hydroxyethyl.

As used herein, the term “C₁-C₈aloalkyl” refers a C₁-C₄alkyl radical asgenerally defined above substituted by one or more of the same ordifferent halogen atoms. Examples of C₁-C₈haloalkyl include, but are notlimited to trifluoromethyl.

As used herein, the term “C₁-C₈alkoxy” refers to a radical of theformula -0R_(a) where R_(a) is a C₁-C₈alkyl radical as generally definedabove. The terms “C₁-C₆alkoxy”, “C₁-C₈alkoxy” and “C₁-C₃alkoxy” are tobe construed accordingly. Examples of C₁-C₈alkoxy include, but are notlimited to, methoxy, ethoxy, 1-methylethoxy (iso-propoxy), and propoxy.

As used herein, the term “C₂-C₆alkenyl” refers to a straight or branchedhydrocarbon chain radical group consisting solely of carbon and hydrogenatoms, containing at least one double bond that can be of either the(E)- or (Z)-configuration, having from two to six carbon atoms, which isattached to the rest of the molecule by a single bond. The term“C₂-C₃alkenyl” is to be construed accordingly. Examples of C₂-C₆alkenylinclude, but are not limited to, ethenyl (vinyl), prop-1-enyl,prop-2-enyl (allyl), but-1-enyl.

As used herein, the term “C₂-C₆alkenyloxy” refers to a radical of theformula —OR_(a) where R_(a) is a C₂-C₆alkenyl radical as generallydefined above.

As used herein, the term “C₂-C₆alkynyl” refers to a straight or branchedhydrocarbon chain radical group consisting solely of carbon and hydrogenatoms, containing at least one triple bond, having from two to sixcarbon atoms, and which is attached to the rest of the molecule by asingle bond. The term “C₂-C₃alkynyl” is to be construed accordingly.Examples of C₂-C₆alkynyl include, but are not limited to, ethynyl,prop-1-ynyl, but-1-ynyl.

As used herein, the term “C₂-C₆alkynyloxy” refers to a radical of theformula —OR_(a) where R_(a) is a C₂-C₆alkynyl radical as generallydefined above.

As used herein, the term “C₁-C₆alkoxyC₁-C₆alkyl” refers to a radical ofthe formula R_(b)OR_(a)O— wherein R_(b) is a C₁-C₆alkyl radical asgenerally defined above, and R_(a) is a C₁-C₆alkylene radical asgenerally defined above.

As used herein, the term “C₁-C₆alkoxyC₁-C₃alkoxy” refers to a radical ofthe formula R_(b)OR_(a)O— wherein R_(b) is a C₁-C₆alkyl radical asgenerally defined above, and R_(a) is a C₁-C₃alkyl radical as generallydefined above.

As used herein, the term “C₁-C₆alkoxycarbonyl” refers to a radical ofthe formula R_(a)OC(O)—, wherein R_(a) is a C₁-C₆alkyl radical asgenerally defined above.

As used herein, the term “C₁-C₆alkoxycarbonylC₁-C₆alkyl” refers to aradical of the formula R_(a)OC(O)R_(b)—, wherein R_(a) is a C₁-C₆alkylradical as generally defined above, and R_(b) is a C₁-C₄alkylene radicalas generally defined above.

As used herein, the term “C₁-C₆alkoxycarbonyloxyC₁-C₄alkyl” refers to aradical of the formula R_(a)OC(O)R_(b)—, wherein R_(a) is a C₁-C₆alkylradical as generally defined above, and R_(b) is a C₁-C₄alkylene radicalas generally defined above. Examples of C₁-C₆alkoxycarbonyloxyC₁-C₄alkylinclude, but are not limited to 1-methoxycarbonyloxy-ethyl and1-methoxycarbonyloxy-methyl.

As used herein, the term “C₁-C₆alkylcarbonyloxyC₁-C₄alkyl” refers to aradical of the formula R_(a)OC₂R_(b)—, wherein R_(a) is a C₁-C₆alkylradical as generally defined above, and R_(b) is a C₁-C₄alkylene radicalas generally defined above. Examples of C₁-C₆alkylcarbonyloxyC₁-C₄alkylinclude, but are not limited to 1-methylcarbonyloxy-methyl.

As used herein, the term “C₁-C₆alkylsulfanyl” refers to a radical of theformula RaS—, wherein R_(a) is a C₁-C₆alkyl radical as generally definedabove.

As used herein, the term “di(C₁-C₆alkyl)amino” refers to a radical ofthe formula (R_(a))(R_(b))N—, wherein R_(a) and R_(b) are eachindividually a C₁-C₆alkyl radical as generally defined above. Examplesof di(C₁-C₆alkyl)amino include, but are not limited to dimethylamino anddiethylamino. As used herein, the term “C₃-C₈cycloalkyl” refers to aradical which is a monocyclic saturated ring system and which contains 3to 8 carbon atoms. The terms “C₃-C₆cycloalkyl”, “C₃-C₄cycloalkyl” are tobe construed accordingly. Examples of C₃-C₆cycloalkyl include, but arenot limited to, cyclopropyl, 1-methylcyclopropyl, 2-methylcyclopropyl,cyclobutyl, 1-methylcyclobutyl, 1,1-dimethylcyclobutyl,2-methylcyclobutyl, and 2,2-dimethylcyclobutyl. As used herein, the term“C₃-C₈cycloalkylC₁-C₂alkyl” refers to a C₃-C₈cycloalkyl ring attached tothe rest of the molecule by a C₁-C₂alkylene linker as defined above.

As used herein, the term “phenylC₁-C₃alkyl” refers to a phenyl ringattached to the rest of the molecule by a C₁-C₃alkylene linker asdefined above.

As used herein, the term “phenylC₁-C₃alkoxyC₁-C₃alkyl” refers to aradical of the formula R_(c)R_(b)OR_(a)—, wherein R_(a) and R_(b) is areeach independently a C₁-C₃alkylene radical as generally defined aboveand R_(c) is a phenyl ring. Examples of phenylC₁-C₃alkoxyC₁-C₃alkylinclude, but are not limited to benzyloxymethyl and 1-benzyloxyethyl.

As used herein, the term “heteroaryl” refers to a 5- or 6-memberedaromatic monocyclic ring radical which comprises 1, 2, 3 or 4heteroatoms individually selected from nitrogen, oxygen and sulfur.Examples of heteroaryl include, but are not limited to, furanyl,pyrrolyl, thienyl, pyrazolyl, imidazolyl, thiazolyl, isothiazolyl,oxazolyl, isoxazolyl, triazolyl, tetrazolyl, pyrazinyl, pyridazinyl,pyrimidyl or pyridyl.

As used herein, the term “heteroarylC₁-C₂alkyl” refers to a heteroarylring attached to the rest of the molecule by a C₁-C₂alkylene linker asdefined above.

As used herein, the term “heterocyclyl” refers to a stable 4-, 5- or6-membered non-aromatic monocyclic ring which comprises 1, 2 or 3heteroatoms, wherein the heteroatoms are individually selected fromnitrogen, oxygen and sulfur. The heterocyclyl radical may be bonded tothe rest of the molecule via a carbon atom or heteroatom. Examples ofheterocyclyl include, but are not limited to, aziridinyl, azetidinyl,oxetanyl, thietanyl, tetrahydrofuryl, pyrrolidinyl, pyrazolidinyl,imidazolidnyl, piperidinyl, piperazinyl, morpholinyl, dioxolanyl,dithiolanyl and thiazolidinyl.

As used herein, the term “heterocyclylC₁-C₂alkyl” refers to aheterocyclyl ring attached to the rest of the molecule by aC₁-C₂alkylene linker as defined above.

As used herein, a “spirocyclic carbobi- or carbotri-cyclyl ring” is anon-aromatic bicyclic ring system comprising two rings joined togetherat one carbon atom, i.e., sharing one carbon atom. Examples of aspirocyclic carbobi- or carbotri-cyclyl ring system include, but are notlimited to, spiro[3.3]heptanyl, spiro[3.4]octanyl, spiro[4.5]decanyl,spiro[cyclobutan-1,2′-indanyl], or spiro[cyclopentane-1,2′-tetralinyl].

The presence of one or more possible asymmetric carbon atoms in acompound of formula (I) means that the compounds may occur in opticallyisomeric forms, i.e., enantiomeric or diastereomeric forms. Also,atropisomers may occur as a result of restricted rotation about a singlebond. Formula (I) is intended to include all those possible isomericforms and mixtures thereof. The present invention includes all thosepossible isomeric forms and mixtures thereof for a compound of formula(I). Likewise, formula (I) is intended to include all possibletautomers. The present invention includes all possible tautomeric formsfor a compound of formula (I).

In each case, the compounds of formula (I) according to the inventionare in free form, in oxidized form as an N-oxide, or in salt form, e.g.,an agronomically usable salt form.

N-oxides are oxidized forms of tertiary amines or oxidized forms ofnitrogen-containing heteroaromatic compounds. They are described forinstance in the book “Heterocyclic N-oxides” by A. Albini and S. Pietra,CRC Press, Boca Raton (1991).

The following list provides definitions, including preferreddefinitions, for substituents R¹, R², R³, R⁴, X and Y with reference tocompounds of formula (I). For any one of these substituents, any of thedefinitions given below may be combined with any definition of any othersubstituent given below or elsewhere in this document.

Y is C—F, C—H or N. In one embodiment, Y is C—F. In another embodiment,Y is C—H. In a further embodiment, Y is N.

R¹ is hydrogen, C₁-C₆alkyl, C₁-C₆alkoxy, C₁-C₆haloalkyl,C₁-C₆hydroxyalkyl, C₁-C₆alkoxyC₁-C₆alkyl, C₃-C₆cycloalkyl,C₁-C₆alkoxyC₁-C₃alkoxy, C₁-C₆alkoxycarbonyl,C₁-C₆alkoxycarbonylC₁-C₆alkyl, C₁-C₆alkoxycarbonyloxyC₁-C₄alkyl,C₁-C₆alkycarbonyloxyC₁-C₄alkyl, C₂-C₆alkenyloxy, C₂-C₆alkynyloxy,C₁-C₆alkylsulfanyl, di(C₁-C₆alkyl)amino, phenyl, phenylC₁-C₃alkyl,phenylC₁-C₃alkoxyC₁-C₃alkyl, phenoxy, or heteroaryl, wherein theheteroaryl is a 5- or 6-membered aromatic monocyclic ring comprising 1or 2 heteroatoms individually selected from nitrogen, oxygen and sulfur.

Preferably, R¹ is hydrogen, C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄haloalkyl,C₁-C₄hydroxyalkyl, C₁-C₃alkoxyC₁-C₄alkyl, C₃-C₆cycloalkyl,C₁-C₄alkoxyC₁-C₃alkoxy, C₁-C₃alkoxycarbonyl,C₁-C₃alkoxycarbonylC₁-C₄alkyl, C₁-C₄alkoxycarbonyloxyC₁-C₃alkyl,C₁-C₄alkycarbonyloxyC₁-C₃alkyl, C₃-C₅alkynyloxy, C₁-C₄alkylsulfanyl,di(C₁-C₄alkyl)amino, phenyl, phenylC₁-C₃alkyl, phenylC₁-C₃alkoxyC₁-C₅C₃alkyl, phenoxy, or heteroaryl, wherein the heteroaryl is a 5- or6-membered aromatic monocyclic ring comprising 1 or 2 heteroatomsindividually selected from nitrogen, oxygen and sulfur.

More preferably, R¹ is hydrogen, C₁-C₃alkyl, C₁-C₃alkoxy,C₁-C₃haloalkyl, C₁-C₃hydroxyalkyl, methoxyC₁-C₄alkyl, C₃-C₄cycloalkyl,C₁-C₂alkoxyC₁-C₂alkoxy, C₁-C₃alkoxycarbonyl, methoxycarbonylC₁-C₃alkyl,C₁-C₂alkoxycarbonyloxyC₁-C₂alkyl, C₁-C₂alkycarbonyloxyC₁-C₂alkyl,C₃-C₄alkynyloxy, C₁-C₃alkylsulfanyl, diethylamino, phenyl, benzyl,phenoxy, benzyloxyC₁-C₂alkyl, or heteroaryl, wherein the heteroaryl is a5- or 6-membered aromatic monocyclic ring comprising a single heteroatomselected from oxygen and sulfur.

Even more preferably, R¹ is hydrogen, methyl, ethyl, methoxy, ethoxy,fluoromethyl, chloromethyl, bromomethyl, 2,2,2-trifuoroethyl,1-hydroxyethyl, methoxymethyl, 1-methoxyethyl, 1-ethoxymethyl,1-methoxy-1-methylethyl, cyclopropyl, methoxyethoxy, ethoxycarbonyl,2-methoxy-2-oxo-ethyl, 2-methoxy-oxo-ethyl, 2-methoxy-oxo-propyl,propargyloxy, 1-methoxycarbonyloxy-ethyl, 1-ethoxycarbonyloxy-ethyl,1-methylcarbonyloxy-ethyl, methylcarbonyloxymethyl, methylsulfanyl,ethylsulfanyl, isopropylsulfanyl, diethylamino, phenyl, benzyl, phenoxy,benzyloxymethyl, 1-benzyloxyethyl, 2-furanyl, or 2-thiophenyl.

More preferably still, R¹ is hydrogen, methyl, ethyl, methoxy, ethoxy,fluoromethyl, 2,2,2-trifuoroethyl, 1-hydroxyethyl, 1-ethoxymethyl,cyclopropyl, methoxyethoxy, 2-methoxy-2-oxo-ethyl, 2-methoxy-oxo-ethyl,2-methoxy-oxo-propyl, propargyloxy, 1-methoxycarbonyloxy-ethyl,1-ethoxycarbonyloxy-ethyl, 1-methylcarbonyloxy-ethyl,methylcarbonyloxymethyl, isopropylsulfanyl, diethylamino, phenyl,benzyl, phenoxy, benzyloxymethyl, 1-benzyloxyethyl, 2-furanyl, or2-thiophenyl.

In a particular set of embodiments, R¹ is hydrogen, C₁-C₆alkyl,C₁-C₆alkoxy, C₁-C₆haloalkyl, C₁-C₆alkoxyC₁-C₆alkyl, C₃-C₆cycloalkyl,C₁-C₆alkoxyC₁-C₃alkoxy, C₁-C₆alkoxycarbonyl,C₁-C₆alkoxycarbonylC₁-C₄alkyl, C₂-C₆alkenyloxy, C₂-C₆alkynyloxy,C₁-C₆alkylsulfanyl, phenyl, phenoxy, or heteroaryl, wherein theheteroaryl is a 5- or 6-membered aromatic monocyclic ring comprising 1or 2 heteroatoms individually selected from nitrogen, oxygen and sulfur.

Preferably, R¹ is hydrogen, C₁-C₄alkyl, C₁-C₄alkoxy, C₁-Cahaloalkyl,C₁-C₃alkoxyC₁-C₄alkyl, C₃-C₆cycloalkyl, C₁-C₄alkoxyC₁-C₃alkoxy,C₁-C₃alkoxycarbonyl, C₁-C₃alkoxycarbonylC₁-C₄alkyl, C₃-C₅alkynyloxy,C₁-C₄alkylsulfanyl, phenyl, phenoxy, or heteroaryl, wherein theheteroaryl is a 5- or 6-membered aromatic monocyclic ring comprising 1or 2 heteroatoms individually selected from nitrogen, oxygen and sulfur.

More preferably, R¹ is hydrogen, C₁-C₃alkyl, C₁-C₃alkoxy,C₁-C₃haloalkyl, methoxyC₁-C₄alkyl, C₃-C₄cycloalkyl,C₁-C₂alkoxyC₁-C₂alkoxy, C₁-C₃alkoxycarbonyl, methoxycarbonylC₁-C₃alkyl,C₃-C₄alkynyloxy, C₁-C₃alkylsulfanyl, phenyl, phenoxy, or heteroaryl,wherein the heteroaryl is a 5- or 6-membered aromatic monocyclic ringcomprising a single heteroatom selected from oxygen and sulfur.

Even more preferably, R¹ is hydrogen, methyl, ethyl, methoxy, ethoxy,fluoromethyl, chloromethyl, bromomethyl, 2,2,2-trifuoroethyl,methoxymethyl, 1-methoxyethyl, 1-methoxy-1-methylethyl, cyclopropyl,methoxyethoxy, ethoxycarbonyl, 2-methoxy-2-oxo-ethyl,2-methoxy-oxo-ethyl, 2-methoxy-oxo-propyl, propargyloxy, methylsulfanyl,ethylsulfanyl, isopropylsulfanyl, phenyl, phenoxy, 2-furanyl, or2-thiophenyl.

More preferably still, R¹ is hydrogen, methyl, ethyl, methoxy, ethoxy,fluoromethyl, 2,2,2-trifuoroethyl, cyclopropyl, methoxyethoxy,2-methoxy-2-oxo-ethyl, 2-methoxy-oxo-ethyl, 2-methoxy-oxo-propyl,propargyloxy, isopropylsulfanyl, phenyl, phenoxy, 2-furanyl, or2-thiophenyl.

R² is hydrogen, halogen, cyano, C₁-C₄alkyl, C₁-C₄alkoxy, C₁-Cahaloalkyl,or HC(O)NH—. Preferably, R² is hydrogen, halogen, C₁-C₃alkyl,C₁-C₃alkoxy, C₁-C₂haloalkyl, or HC(O)NH—, more preferably halogen,C₁-C₂alkyl, C₁-C₂alkoxy, or HC(O)NH—. Even more preferably, R² ischloro, bromo, methyl, methoxy, or HC(O)NH—. Even more preferably, R² ismethyl or HC(O)NH—, and most preferably methyl.

R³ is C₁-C₈alkyl, C₁-C₈haloalkyl, C₁-C₈alkoxy, C₃-C₈cycloalkyl,C₃-C₈cycloalkylC₁-C₂alkyl (wherein the cycloalkyl groups are optionallysubstituted with 1 to 3 groups represented by R⁴), phenyl,phenylC₁-C₂alkyl, heteroaryl, heteroarylC₁-C₂alkyl, wherein theheteroaryl is a 5- or 6-membered aromatic monocyclic ring comprising 1,2, 3 or 4 heteroatoms individually selected from nitrogen, oxygen andsulfur, heterocyclyl, heterocyclylC₁-C₂alkyl, wherein the heterocyclylis a 4-, 5- or 6-membered non-aromatic monocyclic ring comprising 1, 2or 3 heteroatoms individually selected from nitrogen, oxygen and sulfur,or a 5- to 10-membered non-aromatic spirocyclic carbobi- orcarbotri-cyclyl ring system optionally comprising 1, 2, 3, 4 orheteroatoms individually selected from nitrogen, oxygen and sulfur, andwherein said spirocyclic carbobi- or carbotri-cyclyl ring systems areeach optionally bonded to the rest of the molecule through aC₁-C₂alkylene linker.

Preferably, R³ is C₁-C₆alkyl, C₁-Cahaloalkyl, C₁-C₄alkoxy,C₃-C₆cycloalkyl, C₃-C₆cycloalkylC₁-C₂alkyl (wherein the cycloalkylgroups are optionally substituted with 1 to 3 groups represented by R⁴),phenyl, heteroaryl, heteroarylC₁-C₂alkyl, wherein the heteroaryl is a 5-or 6-membered aromatic monocyclic ring comprising 1, 2 or 3 heteroatomsindividually selected from nitrogen, oxygen and sulfur, heterocyclyl,heterocyclylC₁-C₂alkyl, wherein the heterocyclyl is a 4-, 5- or6-membered non-aromatic monocyclic ring comprising 1, 2 or 3 heteroatomsindividually selected from nitrogen, oxygen and sulfur, or a 5- to12-membered non-aromatic spirocyclic carbobi- or carbotri-cyclyl ringsystem optionally comprising 1, 2 or 3 heteroatoms individually selectedfrom nitrogen, oxygen and sulfur, and wherein said spirocyclic carbobi-or carbotri-cyclyl ring systems are each optionally bonded to the restof the molecule through a C₁-C₂alkylene linker. More preferably, R³ isC₁-C₄alkyl, C₁-C₃alkoxy, C₃-C₆cycloalkyl, C₃-C₆cycloalkylC₁-C₂alkyl(wherein the cycloalkyl groups are optionally substituted with 1 to 3groups represented by R⁴), phenyl, heteroaryl wherein the heteroaryl isa 5- or 6-membered aromatic monocyclic ring comprising 1, 2 or 3heteroatoms individually selected from nitrogen, oxygen and sulfur,heterocyclyl wherein the heterocyclyl is a 4-, 5- or 6-memberednon-aromatic monocyclic ring comprising 1, 2 or 3 heteroatomsindividually selected from nitrogen, oxygen and sulfur, or a 5- to12-membered non-aromatic spirocyclic carbobi- or carbotri-cyclyl ringsystem optionally comprising a single heteroatom selected from nitrogen,oxygen and sulfur.

Even more preferably, R³ is C₃-C₆cycloalkyl, wherein the cycloalkylgroups are optionally substituted with 1 or 2 groups represented by R⁴,or R³ is a 6- to 10-membered non-aromatic spirocyclic carbobi-cyclylring system.

More preferably still, R³ is C₃-Cacycloalkyl, wherein the cycloalkylgroups are optionally substituted with 1 or 2 groups represented by R⁴,or R³ is a 6- to 8-membered non-aromatic spirocyclic carbobi-cyclyl ringsystem.

Even more preferably still, R³ is cyclobutyl, 2,2-dimethylcyclobutyl orspiro[3.4]octanyl, and most preferably, cyclobutyl,2,2-dimethylcyclobutyl, or spiro[3.4]octan-3-yl.

R⁴ is halogen, C₁-C₄alkyl, C₁-C₄alkoxy, or C₁-C₄haloalkyl. Preferably,R⁴ is halogen, C₁-C₃alkyl, C₁-C₃alkoxy, C₁-C₂haloalkyl, more preferably,halogen, C₁-C₃alkyl, C₁-C₃alkoxy, or C₁-C₃haloalkyl. Even morepreferably, R⁴ is C₁-C₃alkyl, more preferably still, methyl, ethyl orisopropyl, and most preferably R⁴ is methyl.

X is N or C—H. In one embodiment, X is N. In another embodiment, X isC—H.

In a compound of formula (I) according to the present invention,preferably: R¹ is hydrogen, C₁-C₆alkyl, C₁-C₆alkoxy, C₁-C₆haloalkyl,C₁-C₆hydroxyalkyl, C₁-C₆alkoxyC₁-C₆alkyl, C₃-C₆cycloalkyl,C₁-C₆alkoxyC₁-C₃alkoxy, C₁-C₆alkoxycarbonyl,C₁-C₆alkoxycarbonylC₁-C₄alkyl, C₁-C₆alkoxycarbonyloxyC₁-C₄alkyl,C₁-C₆alkylcarbonyloxyC₁-C₄alkyl, C₂-C₆alkenyloxy, C₂-C₆alkynyloxy,C₁-C₆alkylsulfanyl, di(C₁-C₆alkyl)amino, phenyl, phenylC₁-C₃alkyl,phenylC₁-C₃alkoxyC₁-C₃alkyl, phenoxy, or heteroaryl, wherein theheteroaryl is a 5- or 6-membered aromatic monocyclic ring comprising 1or 2 heteroatoms individually selected from nitrogen, oxygen and sulfur;

R² is methyl;

R³ is C₁-C₈alkyl, C₁-C₈aloalkyl, C₁-C₈alkoxy, C₃-C₈cycloalkyl,C₃-C₈cycloalkylC₁-C₂alkyl (wherein the cycloalkyl groups are optionallysubstituted with 1 to 3 groups represented by R⁴), phenyl,phenylC₁-C₂alkyl, heteroaryl, heteroarylC₁-C₂alkyl, wherein theheteroaryl is a 5- or 6-membered aromatic monocyclic ring comprising 1,2, 3 or 4 heteroatoms individually selected from nitrogen, oxygen andsulfur, heterocyclyl, heterocyclylC₁-C₂alkyl, wherein the heterocyclylis a 4-, 5- or 6-membered non-aromatic monocyclic ring comprising 1, 2or 3 heteroatoms individually selected from nitrogen, oxygen and sulfur,or a 5- to 10-membered non-aromatic spirocyclic carbobi- orcarbotri-cyclyl ring system optionally comprising 1, 2, 3, 4 orheteroatoms individually selected from nitrogen, oxygen and sulfur, andwherein said spirocyclic carbobi- or carbotri-cyclyl ring systems areeach optionally bonded to the rest of the molecule through aC₁-C₂alkylene linker;

R⁴ is halogen, C₁-C₄alkyl, C₁-C₄alkoxy, or C₁-C₄haloalkyl;

X is C N; and

Y is C—F.

More preferably, R¹ is hydrogen, C₁-C₆alkyl, C₁-C₆alkoxy,C₁-C₆haloalkyl, C₁-C₆hydroxyalkyl, C₁-C₆alkoxyC₁-C₆alkyl,C₃-C₆cycloalkyl, C₁-C₆alkoxyC₁-C₃alkoxy, C₁-C₆alkoxycarbonyl,C₁-C₆alkoxycarbonylC₁-C₄alkyl, C₁-C₆alkoxycarbonyloxyC₁-C₄alkyl,C₁-C₆alkylcarbonyloxyC₁-C₄alkyl, C₂-C₆alkynyloxy, C₁-C₆alkylsulfanyl,di(C₁-C₆alkyl)amino, phenyl, phenylC₁-C₃alkyl,phenylC₁-C₃alkoxyC₁-C₃alkyl, phenoxy, or heteroaryl, wherein theheteroaryl is a 5- or 6-membered aromatic monocyclic ring comprising 1or 2 heteroatoms individually selected from nitrogen, oxygen and sulfur;

R² is methyl;

R³ is C₃-C₈cycloalkyl, wherein the cycloalkyl groups are optionallysubstituted with 1 to 3 groups represented by R⁴, or R³ is a 5- to10-membered non-aromatic spirocyclic carbobicyclyl ring systemoptionally comprising 1, 2, 3, 4 or heteroatoms individually selectedfrom nitrogen, oxygen and sulfur, and wherein said spirocyclic carbobi-or carbotri-cyclyl ring systems are each optionally bonded to the restof the molecule through a C₁-C₂alkylene linker;

X is N; and

Y is C—F.

Even more preferably, R¹ hydrogen, C₁-C₃alkyl, C₁-C₃alkoxy,C₁-C₃haloalkyl, C₁-C₃hydroxyalkyl, methoxyC₁-C₄alkyl, C₃-Cacycloalkyl,C₁-C₂alkoxyC₁-C₂alkoxy, C₁-C₃alkoxycarbonyl, methoxycarbonylC₁-C₃alkyl,C₁-C₂alkoxycarbonyloxyC₁-C₂alkyl, C₁-C₂alkylcarbonyloxyC₁-C₂alkyl,C₃-C₄alkynyloxy, C₁-C₃alkylsulfanyl, diethylamino, phenyl, benzyl,phenoxy, benzyloxyC₁-C₂alkyl, or heteroaryl, wherein the heteroaryl is a5- or 6-membered aromatic monocyclic ring comprising a single heteroatomselected from oxygen and sulfur; R² is methyl;

R³ is cyclobutyl, 2,2-dimethylcyclobutyl, or spiro[3.4]octan-3-yl;

X is N; and

Y is C—F.

More preferably still, R¹ is hydrogen, methyl, ethyl, methoxy, ethoxy,fluoromethyl, chloromethyl, bromomethyl, 2,2,2-trifuoroethyl,1-hydroxyethyl, methoxymethyl, 1-methoxyethyl, 1-ethoxymethyl,1-methoxy-1-methylethyl, cyclopropyl, methoxyethoxy, ethoxycarbonyl,2-methoxy-2-oxo-ethyl, 2-methoxy-oxo-ethyl, 2-methoxy-oxo-propyl,propargyloxy, 1-methoxycarbonyloxy-ethyl, 1-ethoxycarbonyloxy-ethyl,1-methylcarbonyloxy-ethyl, methylcarbonyloxy-methyl, methylsulfanyl,ethylsulfanyl, isopropylsulfanyl, diethylamino, phenyl, benzyl, phenoxy,benzyloxymethyl, 1-benzyloxyethyl, 2-furanyl, or 2-thiophenyl;

R² is methyl;

R³ is cyclobutyl, 2,2-dimethylcyclobutyl, or spiro[3.4]octan-3-yl;

X is N; and

Y is C—F.

In a particular set of embodiments, in a compound of formula (I)according to the present invention, preferably:

R¹ is hydrogen, C₁-C₆alkyl, C₁-C₆alkoxy, C₁-C₆haloalkyl,C₁-C₆alkoxyC₁-C₆alkyl, C₃-C₆cycloalkyl, C₁-C₆alkoxyC₁-C₃alkoxy,C₁-C₆alkoxycarbonyl, C₁-C₆alkoxycarbonylC₁-C₄alkyl, C₂-C₆alkenyloxy,C₂-C₆alkynyloxy, C₁-C₆alkylsulfanyl, phenyl, phenoxy, or heteroaryl,wherein the heteroaryl is a 5- or 6-membered aromatic monocyclic ringcomprising 1 or 2 heteroatoms individually selected from nitrogen,oxygen and sulfur;

R² is methyl;

R³ is C₁-C₈alkyl, C₁-C₈haloalkyl, C₁-C₈alkoxy, C₃-C₈cycloalkyl,C₃-C₈cycloalkylC₁-C₂alkyl (wherein the cycloalkyl groups are optionallysubstituted with 1 to 3 groups represented by R⁴), phenyl,phenylC₁-C₂alkyl, heteroaryl, heteroarylC₁-C₂alkyl, wherein theheteroaryl is a 5- or 6-membered aromatic monocyclic ring comprising 1,2, 3 or 4 heteroatoms individually selected from nitrogen, oxygen andsulfur, heterocyclyl, heterocyclylC₁-C₂alkyl, wherein the heterocyclylis a 4-, 5- or 6-membered non-aromatic monocyclic ring comprising 1, 2or 3 heteroatoms individually selected from nitrogen, oxygen and sulfur,or a 5- to 10-membered non-aromatic spirocyclic carbobi- orcarbotri-cyclyl ring system optionally comprising 1, 2, 3, 4 orheteroatoms individually selected from nitrogen, oxygen and sulfur, andwherein said spirocyclic carbobi- or carbotri-cyclyl ring systems areeach optionally bonded to the rest of the molecule through aC₁-C₂alkylene linker;

R⁴ is halogen, C₁-C₄alkyl, C₁-C₄alkoxy, or C₁-C₄haloalkyl; X is CN; and

Y is C—F.

More preferably, R¹ is hydrogen, C₁-C₆alkyl, C₁-C₆alkoxy,C₁-C₆haloalkyl, C₁-C₆alkoxyC₁-C₆alkyl, C₃-C₆cycloalkyl,C₁-C₆alkoxyC₁-C₃alkoxy, C₁-C₆alkoxycarbonyl,C₁-C₆alkoxycarbonylC₁-C₄alkyl, C₂-C₆alkynyloxy, C₁-C₆alkylsulfanyl,phenyl, phenoxy, or heteroaryl, wherein the heteroaryl is a 5- or6-membered aromatic monocyclic ring comprising 1 or 2 heteroatomsindividually selected from nitrogen, oxygen and sulfur;

R² is methyl;

R³ is C₃-C₈cycloalkyl, wherein the cycloalkyl groups are optionallysubstituted with 1 to 3 groups represented by R⁴, or R³ is a 5- to10-membered non-aromatic spirocyclic carbobicyclyl ring systemoptionally comprising 1, 2, 3, 4 or heteroatoms individually selectedfrom nitrogen, oxygen and sulfur, and wherein said spirocyclic carbobi-or carbotri-cyclyl ring systems are each optionally bonded to the restof the molecule through a C₁-C₂alkylene linker;

X is N; and

Y is C—F.

Even more preferably, R¹ hydrogen, C₁-C₃alkyl, C₁-C₃alkoxy,C₁-C₃haloalkyl, methoxyC₁-C₄alkyl, C₃-C₄cycloalkyl,C₁-C₂alkoxyC₁-C₂alkoxy, C₁-C₃alkoxycarbonyl, methoxycarbonylC₁-C₃alkyl,C₃-C₄alkynyloxy, C₁-C₃alkylsulfanyl, phenyl, phenoxy, heteroaryl,wherein the heteroaryl is a 5- or 6-membered aromatic monocyclic ringcomprising a single heteroatom selected from oxygen and sulfur; R² ismethyl;

R³ is cyclobutyl, 2,2-dimethylcyclobutyl, or spiro[3.4]octan-3-yl;

X is N; and

Y is C—F.

More preferably still, R¹ is hydrogen, methyl, ethyl, methoxy, ethoxy,fluoromethyl, chloromethyl, bromomethyl, 2,2,2-trifuoroethyl,methoxymethyl, 1-methoxyethyl, 1-methoxy-1-methylethyl, cyclopropyl,methoxyethoxy, ethoxycarbonyl, 2-methoxy-2-oxo-ethyl,2-methoxy-oxo-ethyl, 2-methoxy-oxo-propyl, propargyloxy, methylsulfanyl,ethylsulfanyl, isopropylsulfanyl, phenyl, phenoxy, 2-furanyl, or2-thiophenyl;

R² is methyl;

R³ is cyclobutyl, 2,2-dimethylcyclobutyl, or spiro[3.4]octan-3-yl;

X is N; and

Y is C—F.

Compounds of the present invention can be made as shown in the followingschemes, in which, unless otherwise stated, the definition of eachvariable is as defined above for a compound of formula (I).

The compounds of formula (I) according to the invention, wherein R¹, R²,R³, X and Y are as defined for formula (I), can be obtained bytransformation of a compound of formula (II), wherein R², R³, X and Yare as defined for formula (I), with a compound of formula (Ill),wherein R¹ is as defined for formula (I) and R¹² is halogen, preferablychloro, either by thermal heating, or with the aid of a base.

This is shown in Scheme 1 below.

The compounds of formula (II), wherein R², R³, X and Y are as definedfor formula (I), can be obtained by transformation of a compound offormula (IV), wherein X and Y are as defined for formula (I), with acompound of formula (V), wherein R² and R³ are as defined for formula(I) and R¹³ is halogen, preferably bromo, either by thermal heating, orwith the aid of a base or under the conditions of the transition metalcatalysed Buchwald-Hartwig amination. This is shown in Scheme 2 below.

The compounds of formula (V), wherein R² and R³ are as defined forformula (I) and R¹³ is halogen, preferably bromo, can be obtained bytransformation of a compound of formula (VI), wherein R² is as definedfor formula (I) and R¹³ is halogen, preferably bromo, and a compound offormula (VII), wherein R³ is as defined for formula (I), either via anintermediate acid chloride or directly with a peptide coupling agent.This is shown in Scheme 3 below.

The compounds of formula (VI), wherein R² is as defined for formula (I)and R¹³ is halogen, preferably bromo, can be obtained by transformationof a compound of formula (VIII), wherein R² is as defined for formula(I), R¹³ is halogen, preferably bromo, and R¹⁴ is C₁-C₆alkyl, and abase. This is shown in Scheme 4 below.

Alternatively, the compounds of formula (II), wherein R², R³, X and Yare as defined for formula (I), can be obtained by transformation of acompound of formula (IX), wherein R², X and Y are as defined for formula(I), with a compound of formula (VII), wherein R³ is as defined forformula (I), either via an intermediate acid chloride or directly withan peptide coupling agent. This is shown in Scheme below.

The compounds of formula (IX), wherein R², X and Y are as defined forformula (I), can be obtained by transformation of a compound of formula(X), wherein R², X and Y are as defined for formula (I) and R¹⁴ isC₁-C₆alkyl, with a base. This is shown in Scheme 6 below.

The compounds of formula (X), wherein R², X, and Y are as defined forformula (I) and R¹⁴ is C₁-C₆alkyl, can be obtained by transformation ofa compound of formula (IV), wherein X and Y are as defined for formula(I), with a compound of formula (VII), wherein R² is as defined forformula (I), R¹² is halogen, preferably bromo, and R¹³ is C₁-C₆alkyl,either by thermal heating, or with the aid of a base or under theconditions of the transition metal catalysed Buchwald-Hartwig amination.This is shown in Scheme 7 below.

Alternatively, the compounds of formula (X), wherein R², X and Y are asdefined for formula (I) and R¹⁴ is C₁-C₆alkyl, can be obtained bytransformation of a compound of formula (XI), wherein X and

Y are as defined for formula (I) and R¹³ is halogen, preferably bromo oriodo, with a compound of formula (XII), wherein R² is as defined forformula (I) and R¹⁴ is C₁-Cealkyl, under the conditions of thetransition metal catalysed Buchwald-Hartwig amination. This is shown inScheme 8 below.

Alternatively, the compounds of formula (II), wherein R², R³, X and Yare as defined for formula (I), can be obtained by transformation of acompound of formula (XI), wherein X and Y are as defined for formula (I)and R¹³ is halogen, preferably bromo or iodo, with a compound of formula(XIII), wherein R² and R³ are as defined for formula (I), either bythermal heating, or with the aid of a base or under the conditions ofthe transition metal catalysed Buchwald-Hartwig amination. This is shownin Scheme 9 below.

Alternatively, the compounds of formula (I) according to the invention,wherein R¹, R², R³, X and Y are as defined for formula (I), can beobtained by transformation of a compound of formula (V), wherein R² andR³ are as defined for formula (I) and R¹³ is halogen, preferably bromo,with a compound of formula (XIV), wherein R¹, X and Y are as defined forformula (I) either by thermal heating, or with the aid of a base orunder the conditions of the transition metal catalysed Buchwald-Hartwigamination. This is shown in Scheme 10 below.

The compounds of formula (XIV), wherein R¹, X and Y are as defined forformula (I), can be obtained by transformation of a compound of formula(XV), wherein X and Y are as defined for formula (I), with a compound offormula (Ill), wherein R¹ is as defined for formula (I) and R¹² ishalogen, preferably chloro, either by thermal heating, or with the aidof a base. This is shown in Scheme 11 below.

Alternatively, the compounds of formula (I), wherein R¹, R², R³, X and Yare as defined for formula (I), can be obtained by transformation of acompound of formula (XVI), wherein R¹, R², X and Y are as defined forformula (I), with a compound of formula (VII), wherein R³ is as definedfor formula (I), either by thermal heating, or with the aid of a base.This is shown in Scheme 12 below.

The compounds of formula (XVI), wherein R¹, R², X and Y are as definedfor formula (I), can be obtained by transformation of a compound offormula (IX), wherein R², X and Y are as defined for formula (I), with acompound of formula (III), wherein R¹ is as defined for formula (I) andR¹² is halogen, preferably chloro, either by thermal heating, or withthe aid of a base. This is shown in Scheme 13 below.

Alternatively, the compounds of formula (XVI), wherein R¹, R², X and Yare as defined for formula (I), can be obtained by transformation of acompound of formula (IX), wherein R², X and Y are as defined for formula(I), with a compound of formula (XVII), wherein R¹ is as defined forformula (I), either by thermal heating, or with the aid of a base. Thisis shown in Scheme 14 below.

Surprisingly, it has now been found that the novel compounds of formula(I) have, for practical purposes, a very advantageous level ofbiological activity for protecting plants against diseases that arecaused by fungi.

The compounds of formula (I) can be used in the agricultural sector andrelated fields of use, e.g., as active ingredients for controlling plantpests or on non-living materials for control of spoilage microorganismsor organisms potentially harmful to man. The novel compounds aredistinguished by excellent activity at low rates of application, bybeing well tolerated by plants and by being environmentally safe. Theyhave very useful curative, preventive and systemic properties and may beused for protecting numerous cultivated plants. The compounds of formula(I) can be used to inhibit or destroy the pests that occur on plants orparts of plants (fruit, blossoms, leaves, stems, tubers, roots) ofdifferent crops of useful plants, while at the same time protecting alsothose parts of the plants that grow later, e.g., from phytopathogenicmicroorganisms.

The present invention further relates to a method for controlling orpreventing infestation of plants or plant propagation material and/orharvested food crops susceptible to microbial attack by treating plantsor plant propagation material and/or harvested food crops wherein aneffective amount a compound of formula (I) is applied to the plants, toparts thereof or the locus thereof.

It is also possible to use the compounds of formula (I) as fungicide.The term “fungicide” as used herein means a compound that controls,modifies, or prevents the growth of fungi. The term “fungicidallyeffective amount” means the quantity of such a compound or combinationof such compounds that is capable of producing an effect on the growthof fungi. Controlling or modifying effects include all deviation fromnatural development, such as killing, retardation and the like, andprevention includes barrier or other defensive formation in or on aplant to prevent fungal infection.

It is also possible to use compounds of formula (I) as dressing agentsfor the treatment of plant propagation material, e.g., seed, such asfruits, tubers or grains, or plant cuttings (e.g., rice), for theprotection against fungal infections, as well as against phytopathogenicfungi occurring in the soil. The propagation material can be treatedwith a composition comprising a compound of formula (I) before planting:seed, e.g., can be dressed before being sown.

The active ingredients according to the invention can also be applied tograins (coating), either by impregnating the seeds in a liquidformulation or by coating them with a solid formulation. The compositioncan also be applied to the planting site when the propagation materialis being planted, e.g., to the seed furrow during sowing. The inventionrelates also to such methods of treating plant propagation material andto the plant propagation material so treated.

Furthermore, the compounds according to present invention can be usedfor controlling fungi in related areas, for example in the protection oftechnical materials, including wood and wood related technical products,in food storage, in hygiene management.

In addition, the invention could be used to protect non-living materialsfrom fungal attack, e.g., lumber, wall boards and paint.

The compounds of formula (I) may be, for example, effective againstfungi and fungal vectors of disease as well as phytopathogenic bacteriaand viruses. These fungi and fungal vectors of disease as well asphytopathogenic bacteria and viruses are for example:

Absidia corymbifera, Alternaria spp, Aphanomyces spp, Ascochyta spp,Aspergillus spp. including A. flavus, A. fumigatus, A. nidulans, A.niger, A. terrus, Aureobasidium spp. including A. pullulans, Blastomycesdermatitidis, Blumeria graminis, Bremia lactucae, Botryosphaeria spp.including B. dothidea, B. obtusa, Botrytis spp. inclusing B. cinerea,Candida spp. including C. albicans, C. glabrata, C. krusei, C.lusitaniae, C. parapsilosis, C. tropicalis, Cephaloascus fragrans,Ceratocystis spp, Cercospora spp. including C. arachidicola,Cercosporidium personatum, Cladosporium spp, Claviceps purpurea,Coccidioides immitis, Cochliobolus spp, Colletotrichum spp. including C.musae, Cryptococcus neoformans, Diaporthe spp, Didymella spp, Drechsleraspp, Elsinoe spp, Epidermophyton spp, Erwinia amylovora, Erysiphe spp.including E. cichoracearum, Eutypa lata, Fusarium spp. including F.culmorum, F. graminearum, F. langsethiae, F. moniliforme, F. oxysporum,F. proliferatum, F. subglutinans, F. solani, Gaeumannomyces graminis,Gibberella fujikuroi, Gloeodes pomigena, Gloeosporium musarum,Glomerella cingulate, Guignardia bidwellii, Gymnosporangiumjuniperi-virginianae, Helminthosporium spp, Hemileia spp, Histoplasmaspp. including H. capsulatum, Laetisaria fuciformis, Leptographiumlindbergi, Leveillula taurica, Lophodermium seditiosum, Microdochiumnivale, Microsporum spp, Monilinia spp, Mucor spp, Mycosphaerella spp.including M. graminicola, M. pomi, Oncobasidium theobromaeon, Ophiostomapiceae, Paracoccidioides spp, Penicillium spp. including P. digitatum,P. italicum, Petriellidium spp, Peronosclerospora spp. Including P.maydis, P. philippinensis and P. sorghi, Peronospora spp, Phaeosphaerianodorum, Phakopsora pachyrhizi, Phellinus igniarus, Phialophora spp,Phoma spp, Phomopsis viticola, Phytophthora spp. including P. infestans,Plasmopara spp. including P. halstedii, P. viticola, Pleospora spp.,Podosphaera spp. including P. leucotricha, Polymyxa graminis, Polymyxabetae, Pseudocercosporella herpotrichoides, Pseudomonas spp,Pseudoperonospora spp. including P. cubensis, P. humuli, Pseudopezizatracheiphila, Puccinia Spp. including P. hordei, P. recondita, P.striiformis, P. triticina, Pyrenopeziza spp, Pyrenophora spp,Pyricularia spp. including P. oryzae, Pythium spp. including P. ultimum,Ramularia spp, Rhizoctonia spp, Rhizomucor pusillus, Rhizopus arrhizus,Rhynchosporium spp, Scedosporium spp. including S. apiospermum and S.prolificans, Schizothyrium pomi, Sclerotinia spp, Sclerotium spp,Septoria spp, including S. nodorum, S. tritici, Sphaerotheca macularis,Sphaerotheca fusca (Sphaerotheca fuliginea), Sporothorix spp,Stagonospora nodorum, Stemphylium spp., Stereum hirsutum, Thanatephoruscucumeris, Thielaviopsis basicola, Tilletia spp, Trichoderma spp.,including T. harzianum, T. pseudokoningii, T. viride, Trichophyton spp,Typhula spp, Uncinula necator, Urocystis spp, Ustilago spp, Venturiaspp. including V. inaequalis, Verticillium spp, and Xanthomonas spp.

Within the scope of present invention, target crops and/or useful plantsto be protected typically comprise perennial and annual crops, such asberry plants for example blackberries, blueberries, cranberries,raspberries and strawberries; cereals for example barley, maize (corn),millet, oats, rice, rye, sorghum triticale and wheat; fibre plants forexample cotton, flax, hemp, jute and sisal; field crops for examplesugar and fodder beet, coffee, hops, mustard, oilseed rape (canola),poppy, sugar cane, sunflower, tea and tobacco; fruit trees for exampleapple, apricot, avocado, banana, cherry, citrus, nectarine, peach, pearand plum; grasses for example Bermuda grass, bluegrass, bentgrass,centipede grass, fescue, ryegrass, St. Augustine grass and Zoysia grass;herbs such as basil, borage, chives, coriander, lavender, lovage, mint,oregano, parsley, rosemary, sage and thyme; legumes for example beans,lentils, peas and soya beans; nuts for example almond, cashew, groundnut, hazelnut, peanut, pecan, pistachio and walnut; palms for exampleoil palm; ornamentals for example flowers, shrubs and trees; othertrees, for example cacao, coconut, olive and rubber; vegetables forexample asparagus, aubergine, broccoli, cabbage, carrot, cucumber,garlic, lettuce, marrow, melon, okra, onion, pepper, potato, pumpkin,rhubarb, spinach and tomato; and vines for example grapes.

The term “useful plants” is to be understood as including also usefulplants that have been rendered tolerant to herbicides like bromoxynil orclasses of herbicides (such as, for example, HPPD inhibitors, ALSinhibitors, for example primisulfuron, prosulfuron and trifloxysulfuron,EPSPS (5-enol-pyrovyl-shikimate-3-phosphate-synthase) inhibitors, GS(glutamine synthetase) inhibitors or PPO (protoporphyrinogen-oxidase)inhibitors) as a result of conventional methods of breeding or geneticengineering. An example of a crop that has been rendered tolerant toimidazolinones, e.g. imazamox, by conventional methods of breeding(mutagenesis) is Clearfield® summer rape (Canola). Examples of cropsthat have been rendered tolerant to herbicides or classes of herbicidesby genetic engineering methods include glyphosate- andglufosinate-resistant maize varieties commercially available under thetrade names RoundupReady®, Herculex I® and LibertyLink®.

The term “useful plants” is to be understood as including also usefulplants which have been so transformed by the use of recombinant DNAtechniques that they are capable of synthesising one or more selectivelyacting toxins, such as are known, for example, from toxin-producingbacteria, especially those of the genus Bacillus.

Examples of such plants are: YieldGard® (maize variety that expresses aCrylA(b) toxin); YieldGard Rootworm® (maize variety that expresses aCryIIIB(b1) toxin); YieldGard Plus® (maize variety that expresses aCrylA(b) and a CryIIIB(b1) toxin); Starlink® (maize variety thatexpresses a Cry9(c) toxin); Herculex I® (maize variety that expresses aCryIF(a2) toxin and the enzyme phosphinothricine N-acetyltransferase(PAT) to achieve tolerance to the herbicide glufosinate ammonium);NuCOTN 33B® (cotton variety that expresses a CrylA(c) toxin); BollgardI® (cotton variety that expresses a CrylA(c) toxin); Bollgard Il®(cotton variety that expresses a CryIA(c) and a CryIIA(b) toxin);VIPCOT® (cotton variety that expresses a VIP toxin); NewLeaf® (potatovariety that expresses a CryIIIA toxin); NatureGard® Agrisure® GTAdvantage (GA21 glyphosate-tolerant trait), Agrisure® CB Advantage (Bt11corn borer (CB) trait), Agrisure® RW (corn rootworm trait) andProtecta®.

The term “crops” is to be understood as including also crop plants whichhave been so transformed by the use of recombinant DNA techniques thatthey are capable of synthesising one or more selectively acting toxins,such as are known, for example, from toxin-producing bacteria,especially those of the genus Bacillus.

Toxins that can be expressed by such transgenic plants include, forexample, insecticidal proteins from Bacillus cereus or Bacilluspopilliae; or insecticidal proteins from Bacillus thuringiensis, such asδ-endotoxins, e.g. Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A,Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), e.g. Vip1,Vip2, Vip3 or Vip3A; or insecticidal proteins of bacteria colonisingnematodes, for example Photorhabdus spp. or Xenorhabdus spp., such asPhotorhabdus luminescens, Xenorhabdus nematophilus; toxins produced byanimals, such as scorpion toxins, arachnid toxins, wasp toxins and otherinsect-specific neurotoxins; toxins produced by fungi, such asStreptomycetes toxins, plant lectins, such as pea lectins, barleylectins or snowdrop lectins; agglutinins; proteinase inhibitors, such astrypsin inhibitors, serine protease inhibitors, patatin, cystatin,papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin,maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolismenzymes, such as 3-hydroxysteroidoxidase,ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidases, ecdysoneinhibitors, HMG-COA-reductase, ion channel blockers, such as blockers ofsodium or calcium channels, juvenile hormone esterase, diuretic hormonereceptors, stilbene synthase, bibenzyl synthase, chitinases andglucanases.

In the context of the present invention there are to be understood byδ-endotoxins, for example Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A,Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for exampleVip1, Vip2, Vip3 or Vip3A, expressly also hybrid toxins, truncatedtoxins and modified toxins. Hybrid toxins are produced recombinantly bya new combination of different domains of those proteins (see, forexample, WO 02/15701). Truncated toxins, for example a truncated Cry1Ab,are known. In the case of modified toxins, one or more amino acids ofthe naturally occurring toxin are replaced. In such amino acidreplacements, preferably non-naturally present protease recognitionsequences are inserted into the toxin, such as, for example, in the caseof Cry3A055, a cathepsin-G-recognition sequence is inserted into a Cry3Atoxin (see WO 03/018810).

Examples of such toxins or transgenic plants capable of synthesisingsuch toxins are disclosed, for example, in EP-A-0 374 753, WO 93/07278,WO 95/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073.

The processes for the preparation of such transgenic plants aregenerally known to the person skilled in the art and are described, forexample, in the publications mentioned above. Cryl-type deoxyribonucleicacids and their preparation are known, for example, from WO 95/34656,EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.

The toxin contained in the transgenic plants imparts to the plantstolerance to harmful insects. Such insects can occur in any taxonomicgroup of insects, but are especially commonly found in the beetles(Coleoptera), two-winged insects (Diptera) and butterflies(Lepidoptera).

Transgenic plants containing one or more genes that code for aninsecticidal resistance and express one or more toxins are known andsome of them are commercially available. Examples of such plants are:YieldGard® (maize variety that expresses a Cry1Ab toxin); YieldGardRootworm® (maize variety that expresses a Cry3Bb1 toxin); YieldGardPlus® (maize variety that expresses a Cry1Ab and a Cry3Bb1 toxin);Starlink® (maize variety that expresses a Cry9C toxin); Herculex I®(maize variety that expresses a Cry1Fa2 toxin and the enzymephosphinothricine N-acetyltransferase (PAT) to achieve tolerance to theherbicide glufosinate ammonium); NuCOTN 33B® (cotton variety thatexpresses a Cry1Ac toxin); Bollgard I® (cotton variety that expresses aCrylAc toxin); Bollgard Il® (cotton variety that expresses a Cry1Ac anda Cry2Ab toxin); VipCot® (cotton variety that expresses a Vip3A and aCry1Ab toxin); NewLeaf® (potato variety that expresses a Cry3A toxin);NatureGard®, Agrisure® GT Advantage (GA21 glyphosate-tolerant trait),Agrisure® CB Advantage (Bt11 corn borer (CB) trait) and Protecta®.

Further examples of such transgenic crops are:

-   1. Bt11 Maize from Syngenta Seeds SAS, Chemin de I′Hobit 27, F-31    790 St. Sauveur, France, registration number C/FR/96/05/10.    Genetically modified Zea mays which has been rendered resistant to    attack by the European corn borer (Ostrinia nubilalis and Sesamia    nonagrioides) by transgenic expression of a truncated Cry1Ab toxin.    Bt11 maize also transgenically expresses the enzyme PAT to achieve    tolerance to the herbicide glufosinate ammonium.-   2. Bt176 Maize from Syngenta Seeds SAS, Chemin de I′Hobit 27, F-31    790 St. Sauveur, France, registration number C/FR/96/05/10.    Genetically modified Zea mays which has been rendered resistant to    attack by the European corn borer (Ostrinia nubilalis and Sesamia    nonagrioides) by transgenic expression of a Cry1Ab toxin. Bt176    maize also transgenically expresses the enzyme PAT to achieve    tolerance to the herbicide glufosinate ammonium.-   3. MIR604 Maize from Syngenta Seeds SAS, Chemin de I′Hobit 27, F-31    790 St. Sauveur, France, registration number C/FR/96/05/10. Maize    which has been rendered insect-resistant by transgenic expression of    a modified Cry3A toxin. This toxin is Cry3A055 modified by insertion    of a cathepsin-G-protease recognition sequence. The preparation of    such transgenic maize plants is described in WO 03/018810.-   4. MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de    Tervuren, B-1150 Brussels, Belgium, registration number C/DE/02/9.    MON 863 expresses a Cry3Bb1 toxin and has resistance to certain    Coleoptera insects.-   5. IPC 531 Cotton from Monsanto Europe S.A. 270-272 Avenue de    Tervuren, B-1150 Brussels, Belgium, registration number C/ES/96/02.-   6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7    B-1160 Brussels, Belgium, registration number C/NL/00/10.    Genetically modified maize for the expression of the protein Cry1F    for achieving resistance to certain Lepidoptera insects and of the    PAT protein for achieving tolerance to the herbicide glufosinate    ammonium.-   7. NK603×MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de    Tervuren, B-1150 20 Brussels, Belgium, registration number    C/GB/02/M3/03. Consists of conventionally bred hybrid maize    varieties by crossing the genetically modified varieties NK603 and    MON 810. NK603×MON 810 Maize transgenically expresses the protein    CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts    tolerance to the herbicide Roundup® (contains glyphosate), and also    a Cry1Ab toxin obtained from Bacillus thuringiensis subsp. kurstaki    which brings about tolerance to certain Lepidoptera, include the    European corn borer.

The term “locus” as used herein means fields in or on which plants aregrowing, or where seeds of cultivated plants are sown, or where seedwill be placed into the soil. It includes soil, seeds, and seedlings, aswell as established vegetation.

The term “plants” refers to all physical parts of a plant, includingseeds, seedlings, saplings, roots, tubers, stems, stalks, foliage, andfruits.

The term “plant propagation material” is understood to denote generativeparts of the plant, such as seeds, which can be used for themultiplication of the latter, and vegetative material, such as cuttingsor tubers, for example potatoes. There may be mentioned for exampleseeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes andparts of plants. Germinated plants and young plants which are to betransplanted after germination or after emergence from the soil, mayalso be mentioned. These young plants may be protected beforetransplantation by a total or partial treatment by immersion. Preferably“plant propagation material” is understood to denote seeds.

Pesticidal agents referred to herein using their common name are known,for example, from “The Pesticide Manual”, 15th Ed., British CropProtection Council 2009.

The compounds of formula (I) may be used in unmodified form or,preferably, together with the adjuvants conventionally employed in theart of formulation. To this end, they may be conveniently formulated inknown manner to emulsifiable concentrates, coatable pastes, directlysprayable or dilutable solutions or suspensions, dilute emulsions,wettable powders, soluble powders, dusts, granulates, and alsoencapsulations e.g. in polymeric substances. As with the type of thecompositions, the methods of application, such as spraying, atomising,dusting, scattering, coating or pouring, are chosen in accordance withthe intended objectives and the prevailing circumstances. Thecompositions may also contain further adjuvants such as stabilizers,antifoams, viscosity regulators, binders or tackifiers as well asfertilizers, micronutrient donors or other formulations for obtainingspecial effects. Suitable carriers and adjuvants, e.g., for agriculturaluse, can be solid or liquid and are substances useful in formulationtechnology, e.g. natural or regenerated mineral substances, solvents,dispersants, wetting agents, tackifiers, thickeners, binders orfertilizers. Such carriers are for example described in WO 97/33890.

The compounds of formula (I) are normally used in the form ofcompositions and can be applied to the crop area or plant to be treated,simultaneously or in succession with further compounds. These furthercompounds can be, e.g., fertilizers or micronutrient donors or otherpreparations, which influence the growth of plants. They can also beselective herbicides or non-selective herbicides as well asinsecticides, fungicides, bactericides, nematicides, molluscicides ormixtures of several of these preparations, if desired together withfurther carriers, surfactants or application promoting adjuvantscustomarily employed in the art of formulation.

The compounds of formula (I) may be used in the form of (fungicidal)compositions for controlling or protecting against phytopathogenicmicroorganisms, comprising as active ingredient at least one compound offormula (I) or of at least one preferred individual compound asabove-defined, in free form or in agrochemically usable salt form, andat least one of the above-mentioned adjuvants. The invention provides acomposition, preferably a fungicidal composition, comprising at leastone compound formula (I) an agriculturally acceptable carrier andoptionally an adjuvant. An agricultural acceptable carrier is forexample a carrier that is suitable for agricultural use. Agriculturalcarriers are well known in the art. Preferably, said composition maycomprise at least one or more pesticidally active compounds, for examplean additional fungicidal active ingredient in addition to the compoundof formula (I).

The compound of formula (I) may be the sole active ingredient of acomposition or it may be admixed with one or more additional activeingredients such as a pesticide, fungicide, synergist, herbicide orplant growth regulator where appropriate. An additional activeingredient may, in some cases, result in unexpected synergisticactivities.

Examples of suitable additional active ingredients include the followingacycloamino acid fungicides, aliphatic nitrogen fungicides, amidefungicides, anilide fungicides, antibiotic fungicides, aromaticfungicides, arsenical fungicides, aryl phenyl ketone fungicides,benzamide fungicides, benzanilide fungicides, benzimidazole fungicides,benzothiazole fungicides, botanical fungicides, bridged diphenylfungicides, carbamate fungicides, carbanilate fungicides, conazolefungicides, copper fungicides, dicarboximide fungicides, dinitrophenolfungicides, dithiocarbamate fungicides, dithiolane fungicides, furamidefungicides, furanilide fungicides, hydrazide fungicides, imidazolefungicides, mercury fungicides, morpholine fungicides, organophosphorousfungicides, organotin fungicides, oxathiin fungicides, oxazolefungicides, phenylsulfamide fungicides, polysulfide fungicides, pyrazolefungicides, pyridine fungicides, pyrimidine fungicides, pyrrolefungicides, quaternary ammonium fungicides, quinoline fungicides,quinone fungicides, quinoxaline fungicides, strobilurin fungicides,sulfonanilide fungicides, thiadiazole fungicides, thiazole fungicides,thiazolidine fungicides, thiocarbamate fungicides, thiophene fungicides,triazine fungicides, triazole fungicides, triazolopyrimidine fungicides,urea fungicides, valinamide fungicides, and zinc fungicides. Examples ofsuitable additional active ingredients also include the following:petroleum oils, 1,1-bis(4-chlorophenyl)-2-ethoxyethanol,2,4-dichlorophenyl benzenesulfonate, 2-fluoro-N-methyl-N-1-10naphthylacetamide, 4-chlorophenyl phenyl sulfone, acetoprole,aldoxycarb, amidithion, amidothioate, amiton, amiton hydrogen oxalate,amitraz, aramite, arsenous oxide, azobenzene, azothoate, benomyl,benoxafos, benzyl benzoate, bixafen, brofenvalerate, bromocyclen,bromophos, bromopropylate, buprofezin, butocarboxim, butoxycarboxim,butylpyridaben, calcium polysulfide, camphechlor, carbanolate,carbophenothion, cymiazole, chinomethionat, chlorbenside, chlordimeform,chlordimeform hydrochloride, chlorfenethol, chlorfenson,chlorfensulfide, chlorobenzilate, chloromebuform, chloromethiuron,chloropropylate, chlorthiophos, cinerin I, cinerin II, cinerins,closantel, coumaphos, crotamiton, crotoxyphos, cufraneb, cyanthoate,DCPM, DDT, demephion, demephion-O, demephion-S, demeton-methyl,demeton-O, demeton-O-methyl, demeton-S, demeton-S-methyl,demeton-S-methylsulfon, dichlofluanid, dichlorvos, dicliphos,dienochlor, dimefox, dinex, dinex-diclexine, dinocap-4, dinocap-6,dinocton, dinopenton, dinosulfon, dinoterbon, dioxathion, diphenylsulfone, disulfiram,

DNOC, dofenapyn, doramectin, endothion, eprinomectin, ethoate-methyl,etrimfos, fenazaflor, fenbutatin oxide, fenothiocarb, fenpyrad,fenpyroximate, fenpyrazamine, fenson, fentrifanil, flubenzimine,flucycloxuron, fluenetil, fluorbenside, FMC 1137, formetanate,formetanate hydrochloride, formparanate, gamma-HCH, glyodin, halfenprox,hexadecyl cyclopropanecarboxylate, isocarbophos, jasmolin I, jasmolinII, jodfenphos, lindane, malonoben, mecarbam, mephosfolan, mesulfen,methacrifos, methyl bromide, metolcarb, mexacarbate, milbemycin oxime,mipafox, monocrotophos, morphothion, moxidectin, naled,4-chloro-2-(2-chloro-2-methyl-propyl)-5-[(6-iodo-3-pyridyl)methoxy]pyridazin-3-one,nifluridide, nikkomycins, nitrilacarb, nitrilacarb 1:1 zinc chloridecomplex, omethoate, oxydeprofos, oxydisulfoton, pp'-DDT, parathion,permethrin, phenkapton, phosalone, phosfolan, phosphamidon,polychloroterpenes, polynactins, proclonol, promacyl, propoxur,prothidathion, prothoate, pyrethrin I, pyrethrin II, pyrethrins,pyridaphenthion, pyrimitate, quinalphos, quintiofos, R-1492, phosglycin,rotenone, schradan, sebufos, selamectin, sophamide, SSI-121, sulfiram,sulfluramid, sulfotep, sulfur, diflovidazin, tau-fluvalinate, TEPP,terbam, tetradifon, tetrasul, thiafenox, thiocarboxime, thiofanox,thiometon, thioquinox, thuringiensin, triamiphos, triarathene,triazophos, triazuron, trifenofos, trinactin, vamidothion, vaniliprole,bethoxazin, copper dioctanoate, copper sulfate, cybutryne, dichlone,dichlorophen, endothal, fentin, hydrated lime, nabam, quinoclamine,quinonamid, simazine, triphenyltin acetate, triphenyltin hydroxide,crufomate, piperazine, thiophanate, chloralose, fenthion,pyridin-4-amine, strychnine, 1-hydroxy-1H-pyridine-2-thione,4-(quinoxalin-2-ylamino)benzenesulfonamide, 8-hydroxyquinoline sulfate,bronopol, copper hydroxide, cresol, dipyrithione, dodicin, fenaminosulf,formaldehyde, hydrargaphen, kasugamycin, kasugamycin hydrochloridehydrate, nickel bis(dimethyldithiocarbamate), nitrapyrin, octhilinone,oxolinic acid, oxytetracycline, potassium hydroxyquinoline sulfate,probenazole, streptomycin, streptomycin sesquisulfate, tecloftalam,thiomersal, Adoxophyes orana GV, Agrobacterium radiobacter, Amblyseiusspp., Anagrapha falcifera NPV, Anagrus atomus, Aphelinus abdominalis,Aphidius colemani, Aphidoletes aphidimyza, Autographa californica NPV,Bacillus sphaericus Neide, Beauveria brongniartii, Chrysoperla carnea,Cryptolaemus montrouzieri, Cydia pomonella GV, Dacnusa sibirica,Diglyphus isaea, Encarsia formosa, Eretmocerus eremicus, Heterorhabditisbacteriophora and H. megidis, Hippodamia convergens, Leptomastixdactylopii, Macrolophus caliginosus, Mamestra brassicae NPV, Metaphycushelvolus, Metarhizium anisopliae var. acridum, Metarhizium anisopliaevar. anisopliae, Neodiprion sertifer NPV and N. lecontei NPV, Onus spp.,Paecilomyces fumosoroseus, Phytoseiulus persimilis, Steinernemabibionis, Steinernema carpocapsae, Steinernema feltiae, Steinernemaglaseri, Steinernema riobrave, Steinernema riobravis, Steinernemascapterisci, Steinernema spp., Trichogramma spp., Typhlodromusoccidentalis, Verticillium lecanii, apholate, bisazir, busulfan,dimatif, hemel, hempa, metepa, methiotepa, methyl apholate, morzid,penfluron, tepa, thiohempa, thiotepa, tretamine, uredepa,(E)-dec-5-en-1-yl acetate with (E)-dec-5-en-1-ol, (E)-tridec-4-en-1-ylacetate, (E)-6-methylhept-2-en-4-ol,(E,Z)-tetradeca-4,10-dien-1-ylacetate, (Z)-dodec-7-en-1-yl acetate,(Z)-hexadec-11-enal, (Z)-hexadec-11-en-1-yl acetate,(Z)-hexadec-13-en-11-yn-1-yl acetate, (Z)-icos-13-en-10-one,(Z)-tetradec-7-en-1-al, (Z)-tetradec-9-en-1-ol, (Z)-tetradec-9-en-1-ylacetate, (7E,9Z)-dodeca-7,9-dien-1-yl acetate, (9Z,11E)-tetradeca-9,11-dlen-1-yl acetate, (9Z,12E)-tetradeca-9,12-d len-1-y! acetate,14-methyloctadec-1-ene, 4-methylnonan-5-ol with 4-methylnonan-5-one,alpha-multistriatin, brevicomin, codlelure, codlemone, cuelure,disparlure, dodec-8-en-1-yl acetate, dodec-9-en-1-yl acetate, dodeca-8,10-dien-1-yl acetate, dominicalure, ethyl 4-methyloctanoate, eugenol,frontalin, grandlure, grandlure I, grandlure II, grandlure III,grandlure IV, hexalure, ipsdienol, ipsenol, japonilure, lineatin,litlure, looplure, medlure, megatomoic acid, methyl eugenol, muscalure,octadeca-2,13-dien-1-yl acetate, octadeca-3,13-dien-1-yl acetate,orfralure, oryctalure, ostramone, siglure, sordidin, sulcatol,tetradec-11-en-1-yl acetate, trimedlure, trimedlure A, trimedlure B,trimedlure B2, trimedlure C, trunc-call, 2-(octylthio)-ethanol,butopyronoxyl, butoxy(polypropylene glycol), dibutyl adipate, dibutylphthalate, dibutyl succinate, diethyltoluamide, dimethyl carbate,dimethyl phthalate, ethyl hexanediol, hexamide, methoquin-butyl,methylneodecanamide, oxamate, picaridin, 1-dichloro-1-nitroethane,1,1-dichloro-2,2-bis(4-ethylphenyl)ethane, 1,2-dichloropropane with1,3-dichloropropene, 1-bromo-2-chloroethane,2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate, 2,2-dichlorovinyl2-ethylsulfinylethyl methyl phosphate, 2-(1,3-dithiolan-2-yl)phenyldimethylcarbamate, 2-(2-butoxyethoxy)ethyl thiocyanate,2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl methylcarbamate,2-(4-chloro-3,5-xylyloxy)ethanol, 2-chlorovinyl diethyl phosphate,2-imidazolidone, 2-isovalerylindan-1,3-dione,2-methyl(prop-2-ynyl)aminophenyl methylcarbamate, 2-thiocyanatoethyllaurate, 3-bromo-1-chloroprop-1-ene, 3-methyl-1-phenylpyrazol-5-yldimethylcarbamate, 4-methyl(prop-2-ynyl)amino-3,5-xylyl methylcarbamate,5,5-dimethyl-3-oxocyclohex-1-enyl dimethylcarbamate, acethion,acrylonitrile, aldrin, allosamidin, allyxycarb, alpha-ecdysone,aluminium phosphide, aminocarb, anabasine, athidathion, azamethiphos,Bacillus thuringiensis delta endotoxins, barium hexafluorosilicate,barium polysulfide, barthrin, Bayer 22/190, Bayer 22408,beta-cyfluthrin, beta-cypermethrin, bioethanomethrin, biopermethrin,bis(2-chloroethyl) ether, borax, bromfenvinfos, bromo-DDT, bufencarb,butacarb, butathiofos, butonate, calcium arsenate, calcium cyanide,carbon disulfide, carbon tetrachloride, cartap hydrochloride, cevadine,chlorbicyclen, chlordane, chlordecone, chloroform, chloropicrin,chlorphoxim, chlorprazophos, cis-resmethrin, cismethrin, clocythrin,copper acetoarsenite, copper arsenate, copper oleate, coumithoate,cryolite, CS 708, cyanofenphos, cyanophos, cyclethrin, cythioate,d-tetramethrin, DAEP, dazomet, decarbofuran, diamidafos, dicapthon,dichlofenthion, dicresyl, dicyclanil, dieldrin, diethyl5-methylpyrazol-3-yl phosphate, dilor, dimefluthrin, dimetan, dimethrin,dimethylvinphos, dimetilan, dinoprop, dinosam, dinoseb, diofenolan,dioxabenzofos, dithicrofos, DSP, ecdysterone, EI 1642, EMPC, EPBP,etaphos, ethiofencarb, ethyl formate, ethylene dibromide, ethylenedichloride, ethylene oxide, EXD, fenchlorphos, fenethacarb,fenitrothion, fenoxacrim, fenpirithrin, fensulfothion, fenthion-ethyl,flucofuron, fosmethilan, fospirate, fosthietan, furathiocarb, furethrin,guazatine, guazatine acetates, sodium tetrathiocarbonate, halfenprox,HCH, HEOD, heptachlor, heterophos, HHDN, hydrogen cyanide, hyquincarb,IPSP, isazofos, isobenzan, isodrin, isofenphos, isolane, isoprothiolane,isoxathion, juvenile hormone I, juvenile hormone II, juvenile hormoneIII, kelevan, kinoprene, lead arsenate, leptophos, lirimfos,lythidathion, m-cumenyl methylcarbamate, magnesium phosphide, mazidox,mecarphon, menazon, mercurous chloride, mesulfenfos, metam,metam-potassium, metam-sodium, methanesulfonyl fluoride, methocrotophos,methoprene, methothrin, methoxychlor, methyl isothiocyanate,methylchloroform, methylene chloride, metoxadiazone, mirex, naftalofos,naphthalene, NC-170, nicotine, nicotine sulfate, nithiazine,nornicotine, O-5-dichloro-4-iodophenyl O-ethyl ethylphosphonothioate,O,O-diethyl O-4-methyl-2-oxo-2H-chromen-7-yl phosphorothioate,O,O-diethyl 0-6-methyl-2-propylpyrimidin-4-yl phosphorothioate,O,O,O′,O′-tetrapropyl dithiopyrophosphate, oleic acid,para-dichlorobenzene, parathion-methyl, pentachlorophenol,pentachlorophenyl laurate, PH 60-38, phenkapton, phosnichlor, phosphine,phoxim-methyl, pirimetaphos, polychlorodicyclopentadiene isomers,potassium arsenite, potassium thiocyanate, precocene I, precocene II,precocene III, primidophos, profluthrin, promecarb, prothiofos,pyrazophos, pyresmethrin, quassia, quinalphos-methyl, quinothion,rafoxanide, resmethrin, rotenone, kadethrin, ryania, ryanodine,sabadilla), schradan, sebufos, SI-0009, thiapronil, sodium arsenite,sodium cyanide, sodium fluoride, sodium hexafluorosilicate, sodiumpentachlorophenoxide, sodium selenate, sodium thiocyanate, sulcofuron,sulcofuron-sodium, sulfuryl fluoride, sulprofos, tar oils, tazimcarb,TDE, tebupirimfos, temephos, terallethrin, tetrachloroethane, thicrofos,thiocyclam, thiocyclam hydrogen oxalate, thionazin, thiosultap,thiosultap-sodium, tralomethrin, transpermethrin, triazamate,trichlormetaphos-3, trichloronat, trimethacarb, tolprocarb,triclopyricarb, triprene, veratridine, veratrine, XMC, zetamethrin, zincphosphide, zolaprofos, and meperfluthrin, tetramethylfluthrin,bis(tributyltin) oxide, bromoacetamide, ferric phosphate,niclosamide-olamine, tributyltin oxide, pyrimorph, trifenmorph,1,2-dibromo-3-chloropropane, 1,3-dichloropropene,3,4-dichlorotetrahydrothio-phene 1,1-dioxide,3-(4-chlorophenyl)-5-methylrhodanine,5-methyl-6-thioxo-1,3,5-thiadiazinan-3-ylacetic acid,6-isopentenylaminopurine, benclothiaz, cytokinins, DCIP, furfural,isamidofos, kinetin, Myrothecium verrucaria composition,tetrachlorothiophene, xylenols, zeatin, potassium ethylxanthate,acibenzolar, acibenzolar-S-methyl, Reynoutria sachalinensis extract,alpha-chlorohydrin, antu, barium carbonate, bisthiosemi, brodifacoum,bromadiolone, bromethalin, chlorophacinone, cholecalciferol, coumachlor,coumafuryl, coumatetralyl, crimidine, difenacoum, difethialone,diphacinone, ergocalciferol, flocoumafen, fluoroacetamide, flupropadine,flupropadine hydrochloride, norbormide, phosacetim, phosphorus, pindone,pyrinuron, scilliroside, sodium fluoroacetate, thallium sulfate,warfarin, 2-(2-butoxyethoxy)ethyl piperonylate,5-(1,3-benzodioxo1-5-yl)-3-hexylcyclohex-2-enone, farnesol withnerolidol, verbutin, MGK 264, piperonyl butoxide, piprotal, propylisomer, S421, sesamex, sesasmolin, sulfoxide, anthraquinone, coppernaphthenate, copper oxychloride, dicyclopentadiene, thiram, zincnaphthenate, ziram, imanin, ribavirin, mercuric oxide,thiophanate-methyl, azaconazole, bitertanol, bromuconazole,cyproconazole, difenoconazole, diniconazole, epoxiconazole,fenbuconazole, fluquinconazole, flusilazole, flutriafol, furametpyr,hexaconazole, imazalil, imibenconazole, ipconazole, metconazole,myclobutanil, paclobutrazole, pefurazoate, penconazole, prothioconazole,pyrifenox, prochloraz, propiconazole, pyrisoxazole, simeconazole,tebuconazole, tetraconazole, triadimefon, triadimenol, triflumizole,triticonazole, ancymidol, fenarimol, nuarimol, bupirimate, dimethirimol,ethirimol, dodemorph, fenpropidine, fenpropimorph, spiroxamine,tridemorph, cyprodinil, mepanipyrim, pyrimethanil, fenpiclonil,fludioxonil, benalaxyl, furalaxyl, metalaxyl, R-metalaxyl, ofurace,oxadixyl, carbendazim, debacarb, fuberidazole, thiabendazole,chlozolinate, dichlozoline, myclozoline, procymi-done, vinclozoline,boscalid, carboxin, fenfuram, flutolanil, mepronil, oxycarboxin,penthiopyrad, thifluzamide, dodine, iminoctadine, azoxystrobin,dimoxystrobin, enestroburin, fenaminstrobin, flufenoxystrobin,fluoxastrobin, kresoxim-methyl, metominostrobin, trifloxystrobin,orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin,pyraoxystrobin, ferbam, mancozeb, maneb, metiram, propineb, zineb,captafol, captan, fluoroimide, folpet, tolylfluanid, bordeaux mixture,copper oxide, mancopper, oxine-copper, nitrothal-isopropyl, edifenphos,iprobenphos, phosdiphen, tolclofos-methyl, anilazine, benthiavalicarb,blasticidin-S, chloroneb, chlorothalonil, cyflufenamid, cymoxanil,diclocymet, diclomezine, dicloran, diethofencarb, dimethomorph,flumorph, dithianon, ethaboxam, etridiazole, famoxadone, fenamidone,fenoxanil, ferimzone, fluazinam, fluopicolide, flusulfamide,fluxapyroxad, fenhexamid, fosetyl-aluminium, hymexazol, iprovalicarb,cyazofamid, methasulfocarb, metrafenone, pencycuron, phthalide,polyoxins, propamocarb, pyribencarb, proquinazid, pyroquilon,pyriofenone, quinoxyfen, quintozene, tiadinil, triazoxide, tricyclazole,triforine, validamycin, valifenalate, zoxamide, mandipropamid,isopyrazam, sedaxane, benzovindiflupyr, pydiflumetofen,3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid(3′,4′,5′-trifluoro-biphenyl-2-yl)-amide, isoflucypram, isotianil,dipymetitrone,6-ethyl-5,7-dioxo-pyrrolo[4,5][1,4]dithiino[1,2-c]isothiazole-3-carbonitrile,2-(difluoromethyl)-N-[3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide,4-(2,6-difluorophenyl)-6-methyl-5-phenyl-pyridazine-3-carbonitrile,(R)-3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide,4-(2-bromo-4-fluoro-phenyl)-N-(2-chloro-6-fluoro-phenyl)-2,5-dimethyl-pyrazol-3-amine,4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine,fluindapyr, coumethoxystrobin (jiaxiangjunzhi), Ivbenmixianan,dichlobentiazox, mandestrobin,3-(4,4-difluoro-3,4-dihydro-3,3-dimethylisoquinolin-1-yl)quinolone,2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quinolyl)oxy]phenyl]propan-2-ol,oxathiapiprolin, tert-butylN-[6-[[[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate,pyraziflumid, inpyrfluxam, trolprocarb, mefentrifluconazole,ipfentrifluconazole, 2-(d ifluoromethyl)-N-[(3R)-3-ethyl-1 ,1-d imethyl-indan-4-yl]pyridine-3-carboxamide,N′-(2,5-dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine,N′-[4-(4,5-dichlorothiazol-2-yl)oxy-2,5-dimethyl-phenyfl-N-ethyl-N-methyl-formamidine,[2-[3-[2-[1-[2-[3,5-bis(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]thihydroisoxazol-5-yl]-3-chloro-phenyl] methanesulfonate, but-3-ynylN-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate,methylN-R5-[4-(2,4-dimethylphenyl)triazol-2-yl]-2-methyl-phenyflmethyl]carbamate,3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine,pyridachlometyl, 3-(d ifluoromethyl)-1-methyl-N- [1,1,3-trimethylindan-4-Apyrazole-4-carboxamide,1-[2-[[1(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazol-5-one,1-methyl-4-[3-methyl-2-[[2-methyl-4-(3,4,5-trimethylpyrazol-1-yl)phenoxy]methyl]phenyfltetrazol-5-one,aminopyrifen, ametoctradin, amisulbrom, penflufen,(Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide,florylpicoxamid, fenpicoxamid, tebufloquin, ipflufenoquin, quinofumelin,isofetamid,N-[2-[2,4-dichloro-phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide,N-[2-[2-chloro-4-(trifluoromethyl)phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide,benzothiostrobin, phenamacril, 5-amino-1,3,4-thiadiazole-2-thiol zincsalt (2:1), fluopyram, flutianil, fluopimomide, pyrapropoyne,picarbutrazox,2-(difluoromethyl)-N-(3-ethyl-1,1-dimethyl-indan-4-yl)pyridine-3-carboxamide,2-(difluoromethyl)-N-((3R)-1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide,4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile,metyltetraprole, 2-(difluoromethyl)-N-((3R)-1 ,1,3-thrnethyli!Idan-4-yl)pyridine-3-carboxamide, α-(1,1-dirnethylethyD-α-K-(trifluofornethoxy)[1,1-biphenyl]-4-yl]-5-pyfimidinernethanol, fluoxapiprolin, enoxastrobin,4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile,4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-sulfanyl-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy] benzonitrile,4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-thioxo-4H-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile,trinexapac, coumoxystrobin, zhongshengmycin, thiodiazole copper, zincthiazole, amectotractin, iprodione,N-methoxy-N-R4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide,N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-Aphenyflmethyl]propanamide,N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-Aphenyflmethyl]propanamide,1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea,1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-Aphenyl]methyl]urea,3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea,N—R4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-Aphenyl]methyl]propanamide,4,4-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyflmethyl]isoxazolidin-3-one,5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyflisoxazolid in-3-one, ethyl1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate,N,N-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1,2,4-triazol-3-amine,which may be prepared from the methods described in WO 2017/055473, WO2017/055469, WO 2017/093348 and WO 30 2017/118689,2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol (this compound may be prepared from themethods described in WO 2017/029179),2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol(this compound may be prepared from the methods described in WO2017/029179),3-[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile(this compound may be prepared from the methods described in WO2016/156290),3-[2-(1-chlorocyclopropyl)-3-(3-chloro-2-fluoro-phenyl)-2-hydroxy-propyflimidazole-4-carbonitrile(this compound may be prepared from the methods described in WO2016/156290), (4-phenoxyphenyl)methyl2-amino-6-methyl-pyridine-3-carboxylate (this compound may be preparedfrom the methods described in WO 2014/006945),2,6-Dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c]dipyrrole-1,3,5,7(2H,6H)-tetrone(this compound may be prepared from the methods described in WO2011/138281),N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzenecarbothioamide.

N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3yl]-Abenzamide,(Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide(this compound may be prepared from the methods described in WO2018/153707),B′-(2-chloro-5-methyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine,N′-[2-chloro-4-(2-fluorophenoxy)-5-methyl-phenyl]-N-ethyl-N-methyl-formamidine(this compound may be prepared from the methods described in WO2016/202742), 2-(difluoromethyl)-N-[(35)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide (this compound may beprepared from the methods described in WO 2014/095675).

The compounds of the invention may also be used in combination withanthelmintic agents. Such anthelmintic agents include, compoundsselected from the macrocyclic lactone class of compounds such asivermectin, avermectin, abamectin, emamectin, eprinomectin, doramectin,selamectin, moxidectin, nemadectin and milbemycin derivatives asdescribed in EP-357460, EP-444964 and EP-594291. Additional anthelminticagents include semisynthetic and biosynthetic avermectin/milbemycinderivatives such as those described in US-5015630, WO-9415944 andWO-9522552. Additional anthelmintic agents include the benzimidazolessuch as albendazole, cambendazole, fenbendazole, flubendazole,mebendazole, oxfendazole, oxibendazole, parbendazole, and other membersof the class. Additional anthelmintic agents include imidazothiazolesand tetrahydropyrimidines such as tetramisole, levamisole, pyrantelpamoate, oxantel or morantel. Additional anthelmintic agents includeflukicides, such as triclabendazole and clorsulon and the cestocides,such as praziquantel and epsiprantel.

The compounds of the invention may be used in combination withderivatives and analogues of the paraherquamide/marcfortine class ofanthelmintic agents, as well as the antiparasitic oxazolines such asthose disclosed in U.S. Pat. Nos. 5,478,855, 4639771 and DE-19520936.

The compounds of the invention may be used in combination withderivatives and analogues of the general class of dioxomorpholineantiparasitic agents as described in WO-9615121 and also withanthelmintic active cyclic depsipeptides such as those described inWO-9611945, WO-9319053, WO-9325543, EP-626375, EP-382173, WO-9419334,EP-382173, and EP-503538.

The compounds of the invention may be used in combination with otherectoparasiticides; for example, fipronil; pyrethroids; organophosphates;insect growth regulators such as lufenuron; ecdysone agonists such astebufenozide and the like; neonicotinoids such as imidacloprid and thelike.

The compounds of the invention may be used in combination with terpenealkaloids, for example those described in WO 95/19363 or WO 04/72086,particularly the compounds disclosed therein.

Other examples of such biologically active compounds that the compoundsof the invention may be used in combination with include but are notrestricted to the following:

Organophosphates: acephate, azamethiphos, azinphos-ethyl, azinphos-methyl, bromophos, bromophos-ethyl, cadusafos, chlorethoxyphos,chlorpyrifos, chlorfenvinphos, chlormephos, demeton, demeton-S-methyl,demeton-S-methyl sulphone, dialifos, diazinon, dichlorvos, dicrotophos,dimethoate, disulfoton, ethion, ethoprophos, etrimfos, famphur,fenamiphos, fenitrothion, fensulfothion, fenthion, flupyrazofos,fonofos, formothion, fosthiazate, heptenophos, isazophos, isothioate,isoxathion, malathion, methacriphos, methamidophos, methidathion,methyl- parathion, mevinphos, monocrotophos, naled, omethoate,oxydemeton-methyl, paraoxon, parathion, parathion-methyl, phenthoate,phosalone, phosfolan, phosphocarb, phosmet, phosphamidon, phorate,phoxim, pirimiphos, pirimiphos- methyl, profenofos, propaphos,proetamphos, prothiofos, pyraclofos, pyridapenthion, quinalphos,sulprophos, temephos, terbufos, tebupirimfos, tetrachlorvinphos,thimeton, triazophos, trichlorfon, vamidothion.

Carbamates: alanycarb, aldicarb, 2-sec-butylphenyl methylcarbamate,benfuracarb, carbaryl, carbofuran, carbosulfan, cloethocarb,ethiofencarb, fenoxycarb, fenthiocarb, furathiocarb, HCN-801,isoprocarb, indoxacarb, methiocarb, methomyl,5-methyl-m-cumenylbutyryl(methyl)carbamate, oxamyl, pirimicarb,propoxur, thiodicarb, thiofanox, triazamate, UC-51717. Pyrethroids:acrinathin, allethrin, alphametrin, 5-benzyl-3-furylmethyl (E) -(1R)-cis-2,2-dimethyl-3-(2-oxothiolan-3-ylidenemethyl)cyclopropanecarboxylate,bifenthrin, beta -cyfluthrin, cyfluthrin, a-cypermethrin, beta-cypermethrin, bioallethrin, bioallethrin((S)-cyclopentylisomer),bioresmethrin, bifenthrin, NCI-85193, cycloprothrin, cyhalothrin,cythithrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate,ethofenprox, fenfluthrin, fenpropathrin, fenvalerate, flucythrinate,flumethrin, fluvalinate (D isomer), imiprothrin, cyhalothrin,lambda-cyhalothrin, permethrin, phenothrin, prallethrin, pyrethrins(natural products), resmethrin, tetramethrin, transfluthrin,theta-cypermethrin, silafluofen, t-fluvalinate, tefluthrin,tralomethrin, Zeta-cypermethrin.

Arthropod growth regulators: a) chitin synthesis inhibitors:benzoylureas: chlorfluazuron, diflubenzuron, fluazuron, flucycloxuron,flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron,triflumuron, buprofezin, diofenolan, hexythiazox, etoxazole,chlorfentazine; b) ecdysone antagonists: halofenozide, methoxyfenozide,tebufenozide; c) juvenoids: pyriproxyfen, methoprene (includingS-methoprene), fenoxycarb; d) lipid biosynthesis inhibitors:spirodiclofen.

Other antiparasitics: acequinocyl, amitraz, AKD-1022, ANS-118,azadirachtin, Bacillus thuringiensis, bensultap, bifenazate, binapacryl,bromopropylate, BTG-504, BTG-505, camphechlor, cartap, chlorobenzilate,chlordimeform, chlorfenapyr, chromafenozide, clothianidine, cyromazine,diacloden, diafenthiuron, DBI-3204, dinactin,dihydroxymethyldihydroxypyrrolidine, dinobuton, dinocap, endosulfan,ethiprole, ethofenprox, fenazaquin, flumite, MTI- 800, fenpyroximate,fluacrypyrim, flubenzimine, flubrocythrinate, flufenzine, flufenprox,fluproxyfen, halofenprox, hydramethylnon, IKI-220, kanemite, NC-196,neem guard, nidinorterfuran, nitenpyram, SD-35651, WL-108477, pirydaryl,propargite, protrifenbute, pymethrozine, pyridaben, pyrimidifen,NC-1111, R-195, RH-0345, RH-2485,

RYI-210, S-1283, S-1833, SI-8601, silafluofen, silomadine, spinosad,tebufenpyrad, tetradifon, tetranactin, thiacloprid, thiocyclam,thiamethoxam, tolfenpyrad, triazamate, triethoxyspinosyn, trinactin,verbutin, vertalec, YI-5301.

Biological agents: Bacillus thuringiensis ssp aizawai, kurstaki,Bacillus thuringiensis delta endotoxin, baculovirus, entomopathogenicbacteria, virus and fungi.

Bactericides: chlortetracycline, oxytetracycline, streptomycin. Otherbiological agents: enrofloxacin, febantel, penethamate, moloxicam,cefalexin, kanamycin, pimobendan, clenbuterol, omeprazole, tiamulin,benazepril, pyriprole, cefquinome, florfenicol, buserelin, cefovecin,tulathromycin, ceftiour, carprofen, metaflumizone, praziquarantel,triclabendazole. Another aspect of invention is related to the use of acompound of formula (I) or of a preferred individual compound asabove-defined, of a composition comprising at least one compound offormula (I) or at least one preferred individual compound asabove-defined, or of a fungicidal or insecticidal mixture comprising atleast one compound of formula (I) or at least one preferred individualcompound as above-defined, in admixture with other fungicides orinsecticides as described above, for controlling or preventinginfestation of plants, e.g. useful plants such as crop plants,propagation material thereof, e.g. seeds, harvested crops, e.g.,harvested food crops, or non-living materials by insects or byphytopathogenic microorganisms, preferably fungal organisms.

A further aspect of invention is related to a method of controlling orpreventing an infestation of plants, e.g., useful plants such as cropplants, propagation material thereof, e.g. seeds, harvested crops, e.g.harvested food crops, or of non-living materials by insects or byphytopathogenic or spoilage microorganisms or organisms potentiallyharmful to man, especially fungal organisms, which comprises theapplication of a compound of formula (I) or of a preferred individualcompound as above-defined as active ingredient to the plants, to partsof the plants or to the locus thereof, to the propagation materialthereof, or to any part of the non-living materials.

Controlling or preventing means reducing infestation by insects or byphytopathogenic or spoilage microorganisms or organisms potentiallyharmful to man, especially fungal organisms, to such a level that animprovement is demonstrated.

A preferred method of controlling or preventing an infestation of cropplants by phytopathogenic microorganisms, especially fungal organisms,or insects which comprises the application of a compound of formula (I),or an agrochemical composition which contains at least one of saidcompounds, is foliar application. The frequency of application and therate of application will depend on the risk of infestation by thecorresponding pathogen or insect. However, the compounds of formula (I)can also penetrate the plant through the roots via the soil (systemicaction) by drenching the locus of the plant with a liquid formulation,or by applying the compounds in solid form to the soil, e.g., ingranular form (soil application). In crops of water rice such granulatescan be applied to the flooded rice field. The compounds of formula (I)may also be applied to seeds (coating) by impregnating the seeds ortubers either with a liquid formulation of the fungicide or coating themwith a solid formulation.

A formulation, e.g. a composition containing the compound of formula(I), and, if desired, a solid or liquid adjuvant or monomers forencapsulating the compound of formula (I), may be prepared in a knownmanner, typically by intimately mixing and/or grinding the compound withextenders, for example solvents, solid carriers and, optionally, surfaceactive compounds (surfactants).

Advantageous rates of application are normally from 5 g to 2 kg ofactive ingredient (a.i.) per hectare (ha), preferably from 10 g to 1 kga.i./ha, most preferably from 20 g to 600 g a.i./ha. When used as seeddrenching agent, convenient dosages are from 10mg to lg of activesubstance per kg of seeds.

When the combinations of the present invention are used for treatingseed, rates of 0.001 to 50 g of a compound of formula (I) per kg ofseed, preferably from 0.01 to 10 g per kg of seed are generallysufficient.

The compositions of the invention may be employed in any conventionalform, for example in the form of a twin pack, a powder for dry seedtreatment (DS), an emulsion for seed treatment (ES), a flowableconcentrate for seed treatment (FS), a solution for seed treatment (LS),a water dispersible powder for seed treatment (WS), a capsule suspensionfor seed treatment (CF), a gel for seed treatment (GF), an emulsionconcentrate (EC), a suspension concentrate (SC), a suspo-emulsion (SE),a capsule suspension (CS), a water dispersible granule (WG), anemulsifiable granule (EG), an emulsion, water in oil (EO), an emulsion,oil in water (DA/), a micro-emulsion (ME), an oil dispersion (OD), anoil miscible flowable (OF), an oil miscible liquid (OL), a solubleconcentrate (SL), an ultra-low volume suspension (SU), an ultra-lowvolume liquid (UL), a technical concentrate (TK), a dispersibleconcentrate (DC), a wettable powder (WP) or any technically feasibleformulation in combination with agriculturally acceptable adjuvants.

Such compositions may be produced in conventional manner, e.g., bymixing the active ingredients with appropriate formulation inerts(diluents, solvents, fillers and optionally other formulatingingredients such as surfactants, biocides, anti-freeze, stickers,thickeners and compounds that provide adjuvancy effects). Alsoconventional slow release formulations may be employed where longlasting efficacy is intended. Particularly formulations to be applied inspraying forms, such as water dispersible concentrates (e.g. EC, SC, DC,OD, SE, EW, EO and the like), wettable powders and granules, may containsurfactants such as wetting and dispersing agents and other compoundsthat provide adjuvancy effects, e.g. the condensation product offormaldehyde with naphthalene sulphonate, an alkylarylsulphonate, alignin sulphonate, a fatty alkyl sulphate, and ethoxylated alkylphenoland an ethoxylated fatty alcohol.

A seed dressing formulation is applied in a manner known per se to theseeds employing the combination of the invention and a diluent insuitable seed dressing formulation form, e.g., as an aqueous suspensionor in a dry powder form having good adherence to the seeds. Such seeddressing formulations are known in the art. Seed dressing formulationsmay contain the single active ingredients or the combination of activeingredients in encapsulated form, e.g. as slow release capsules ormicrocapsules.

In general, the formulations include from 0.01 to 90% by weight ofactive agent, from 0 to 20% agriculturally acceptable surfactant and 10to 99.99% solid or liquid formulation inerts and adjuvant(s), the activeagent consisting of at least the compound of formula (I) together withcomponent (B) and (C), and optionally other active agents, particularlymicrobiocides or conservatives or the like. Concentrated forms ofcompositions generally contain in between about 2 and 80%, preferablybetween about and 70% by weight of active agent. Application forms offormulation may for example contain from 0.01 to 20% by weight,preferably from 0.01 to 5% by weight of active agent. Whereas commercialproducts will preferably be formulated as concentrates, the end userwill normally employ diluted formulations.

Table 1 below illustrates examples of individual compounds of formula(I) according to the invention.

TABLE 1 Individual compounds of formula (I) according to the inventionCpd c X Y R² R¹ No. X Y R² R¹ 1 CH CH Cl H 411 N CH Cl CH₂OCH₃ 2 CH CHCl CH₃ 412 N CH Cl CH(CH₃)OCH₃ 3 CH CH Cl CH₂CH₃ 413 N CH Cl C(CH₃)₂OCH₃4 CH CH Cl OCH₃ 414 N CH Cl CH₂F 5 CH CH Cl OCH₂CH₃ 415 N CH Cl CH₂Cl 6CH CH Cl CH₂OCH₃ 416 N CH Cl CH₂Br 7 CH CH Cl CH(CH₃)OCH₃ 417 N CH ClCH₂CF₃ 8 CH CH Cl C(CH₃)₂OCH₃ 418 N CH Cl CH₂CO₂CH₃ 9 CH CH Cl CH₂F 419N CH Cl CH₂CH₂CO₂CH₃ 10 CH CH Cl CH₂Cl 420 N CH Cl CH₂CH₂CH₂CO₂CH₃ 11 CHCH Cl CH₂Br 421 N CH Cl cyclopropyl 12 CH CH Cl CH₂CF₃ 422 N CH ClCO₂CH₃ 13 CH CH Cl CH₂CO₂CH₃ 423 N CH Cl CO₂CH₂CH₃ 14 CH CH ClCH₂CH₂CO₂CH₃ 424 N CH Cl Ph 15 CH CH Cl CH₂CH₂CH₂CO₂CH₃ 425 N CH Cl2-furanyl 16 CH CH Cl cyclopropyl 426 N CH Cl 2-thiophenyl 17 CH CH ClCO₂CH₃ 427 N CH Cl OPh 18 CH CH Cl CO₂CH₂CH₃ 428 N CH Cl OCH₂CCH 19 CHCH Cl Ph 429 N CH Cl OCH₂CH₂OCH₃ 20 CH CH Cl 2-furanyl 430 N CH Cl SCH₃21 CH CH Cl 2-thiophenyl 431 N CH Cl SCH₂CH₃ 22 CH CH Cl OPh 432 N CH ClSCH(CH₃)₂ 23 CH CH Cl OCH₂CCH 433 N CH Br H 24 CH CH Cl OCH₂CH₂OCH₃ 434N CH Br CH₃ 25 CH CH Cl SCH₃ 435 N CH Br CH₂CH₃ 26 CH CH Cl SCH₂CH₃ 436N CH Br OCH₃ 27 CH CH Cl SCH(CH₃)₂ 437 N CH Br OCH₂CH₃ 28 CH CH Br H 438N CH Br CH₂OCH₃ 29 CH CH Br CH₃ 439 N CH Br CH(CH₃)OCH₃ 30 CH CH BrCH₂CH₃ 440 N CH Br C(CH₃)₂OCH₃ 31 CH CH Br OCH₃ 441 N CH Br CH₂F 32 CHCH Br OCH₂CH₃ 442 N CH Br CH₂Cl 33 CH CH Br CH₂OCH₃ 443 N CH Br CH₂Br 34CH CH Br CH(CH₃)OCH₃ 444 N CH Br CH₂CF₃ 35 CH CH Br C(CH₃)₂OCH₃ 445 N CHBr CH₂CO₂CH₃ 36 CH CH Br CH₂F 446 N CH Br CH₂CH₂CO₂CH₃ 37 CH CH Br CH₂Cl447 N CH Br CH₂CH₂CH₂CO₂CH₃ 38 CH CH Br CH₂Br 448 N CH Br cyclopropyl 39CH CH Br CH₂CF₃ 449 N CH Br CO₂CH₃ 40 CH CH Br CH₂CO₂CH₃ 450 N CH BrCO₂CH₂CH₃ 41 CH CH Br CH₂CH₂CO₂CH₃ 451 N CH Br Ph 42 CH CH BrCH₂CH₂CH₂CO₂CH₃ 452 N CH Br 2-furanyl 43 CH CH Br cyclopropyl 453 N CHBr 2-thiophenyl 44 CH CH Br CO₂CH₃ 454 N CH Br OPh 45 CH CH Br CO₂CH₂CH₃455 N CH Br OCH₂CCH 46 CH CH Br Ph 456 N CH Br OCH₂CH₂OCH₃ 47 CH CH Br2-furanyl 457 N CH Br SCH₃ 48 CH CH Br 2-thiophenyl 458 N CH Br SCH₂CH₃49 CH CH Br OPh 459 N CH Br SCH(CH₃)₂ 50 CH CH Br OCH₂CCH 460 N CH CH₃ H51 CH CH Br OCH₂CH₂OCH₃ 461 N CH CH₃ CH₃ 52 CH CH Br SCH₃ 462 N CH CH₃CH₂CH₃ 53 CH CH Br SCH₂CH₃ 463 N CH CH₃ OCH₃ 54 CH CH Br SCH(CH₃)₂ 464 NCH CH₃ OCH₂CH₃ 55 CH CH CH₃ H 465 N CH CH₃ CH₂OCH₃ 56 CH CH CH₃ CH₃ 466N CH CH₃ CH(CH₃)OCH₃ 57 CH CH CH₃ CH₂CH₃ 467 N CH CH₃ C(CH₃)₂OCH₃ 58 CHCH CH₃ OCH₃ 468 N CH CH₃ CH₂F 59 CH CH CH₃ OCH₂CH₃ 469 N CH CH₃ CH₂Cl 60CH CH CH₃ CH₂OCH₃ 470 N CH CH₃ CH₂Br 61 CH CH CH₃ CH(CH₃)OCH₃ 471 N CHCH₃ CH₂CF₃ 62 CH CH CH₃ C(CH₃)₂OCH₃ 472 N CH CH₃ CH₂CO₂CH₃ 63 CH CH CH₃CH₂F 473 N CH CH₃ CH₂CH₂CO₂CH₃ 64 CH CH CH₃ CH₂Cl 474 N CH CH₃CH₂CH₂CH₂CO₂CH₃ 65 CH CH CH₃ CH₂Br 475 N CH CH₃ cyclopropyl 66 CH CH CH₃CH₂CF₃ 476 N CH CH₃ CO₂CH₃ 67 CH CH CH₃ CH₂CO₂CH₃ 477 N CH CH₃ CO₂CH₂CH₃68 CH CH CH₃ CH₂CH₂CO₂CH₃ 478 N CH CH₃ Ph 69 CH CH CH₃ CH₂CH₂CH₂CO₂CH₃479 N CH CH₃ 2-furanyl 70 CH CH CH₃ cyclopropyl 480 N CH CH₃2-thiophenyl 71 CH CH CH₃ CO₂CH₃ 481 N CH CH₃ OPh 72 CH CH CH₃ CO₂CH₂CH₃482 N CH CH₃ OCH₂CCH 73 CH CH CH₃ Ph 483 N CH CH₃ OCH₂CH₂OCH₃ 74 CH CHCH₃ 2-furanyl 484 N CH CH₃ SCH₃ 75 CH CH CH₃ 2-thiophenyl 485 N CH CH₃SCH₂CH₃ 76 CH CH CH₃ OPh 486 N CH CH₃ SCH(CH₃)₂ 77 CH CH CH₃ OCH₂CCH 487N CH OCH₃ H 78 CH CH CH₃ OCH₂CH₂OCH₃ 488 N CH OCH₃ CH₃ 79 CH CH CH₃ SCH₃489 N CH OCH₃ CH₂CH₃ 80 CH CH CH₃ SCH₂CH₃ 490 N CH OCH₃ OCH₃ 81 CH CHCH₃ SCH(CH₃)₂ 491 N CH OCH₃ OCH₂CH₃ 82 CH CH OCH₃ H 492 N CH OCH₃CH₂OCH₃ 83 CH CH OCH₃ CH₃ 493 N CH OCH₃ CH(CH₃)OCH₃ 84 CH CH OCH₃ CH₂CH₃494 N CH OCH₃ C(CH₃)₂OCH₃ 85 CH CH OCH₃ OCH₃ 495 N CH OCH₃ CH₂F 86 CH CHOCH₃ OCH₂CH₃ 496 N CH OCH₃ CH₂Cl 87 CH CH OCH₃ CH₂OCH₃ 497 N CH OCH₃CH₂Br 88 CH CH OCH₃ CH(CH₃)OCH₃ 498 N CH OCH₃ CH₂CF₃ 89 CH CH OCH₃C(CH₃)₂OCH₃ 499 N CH OCH₃ CH₂CO₂CH₃ 90 CH CH OCH₃ CH₂F 500 N CH OCH₃CH₂CH₂CO₂CH₃ 91 CH CH OCH₃ CH₂Cl 501 N CH OCH₃ CH₂CH₂CH₂CO₂CH₃ 92 CH CHOCH₃ CH₂Br 502 N CH OCH₃ cyclopropyl 93 CH CH OCH₃ CH₂CF₃ 503 N CH OCH₃CO₂CH₃ 94 CH CH OCH₃ CH₂CO₂CH₃ 504 N CH OCH₃ CO₂CH₂CH₃ 95 CH CH OCH₃CH₂CH₂CO₂CH₃ 505 N CH OCH₃ Ph 96 CH CH OCH₃ CH₂CH₂CH₂CO₂CH₃ 506 N CHOCH₃ 2-furanyl 97 CH CH OCH₃ cyclopropyl 507 N CH OCH₃ 2-thiophenyl 98CH CH OCH₃ CO₂CH₃ 508 N CH OCH₃ OPh 99 CH CH OCH₃ CO₂CH₂CH₃ 509 N CHOCH₃ OCH₂CCH 100 CH CH OCH₃ Ph 510 N CH OCH₃ OCH₂CH₂OCH₃ 101 CH CH OCH₃2-furanyl 511 N CH OCH₃ SCH₃ 102 CH CH OCH₃ 2-thiophenyl 512 N CH OCH₃SCH₂CH₃ 103 CH CH OCH₃ OPh 513 N CH OCH₃ SCH(CH₃)₂ 104 CH CH OCH₃OCH₂CCH 514 N CH NHCHO H 105 CH CH OCH₃ OCH₂CH₂OCH₃ 515 N CH NHCHO CH₃106 CH CH OCH₃ SCH₃ 516 N CH NHCHO CH₂CH₃ 107 CH CH OCH₃ SCH₂CH₃ 517 NCH NHCHO OCH₃ 108 CH CH OCH₃ SCH(CH₃)₂ 518 N CH NHCHO OCH₂CH₃ 109 CH CHNHCHO H 519 N CH NHCHO CH₂OCH₃ 110 CH CH NHCHO CH₃ 520 N CH NHCHOCH(CH₃)OCH₃ 111 CH CH NHCHO CH₂CH₃ 521 N CH NHCHO C(CH₃)₂OCH₃ 112 CH CHNHCHO OCH₃ 522 N CH NHCHO CH₂F 113 CH CH NHCHO OCH₂CH₃ 523 N CH NHCHOCH₂Cl 114 CH CH NHCHO CH₂OCH₃ 524 N CH NHCHO CH₂Br 115 CH CH NHCHOCH(CH₃)OCH₃ 525 N CH NHCHO CH₂CF₃ 116 CH CH NHCHO C(CH₃)₂OCH₃ 526 N CHNHCHO CH₂CO₂CH₃ 117 CH CH NHCHO CH₂F 527 N CH NHCHO CH₂CH₂CO₂CH₃ 118 CHCH NHCHO CH₂Cl 528 N CH NHCHO CH₂CH₂CH₂CO₂CH₃ 119 CH CH NHCHO CH₂Br 529N CH NHCHO cyclopropyl 120 CH CH NHCHO CH₂CF₃ 530 N CH NHCHO CO₂CH₃ 121CH CH NHCHO CH₂CO₂CH₃ 531 N CH NHCHO CO₂CH₂CH₃ 122 CH CH NHCHOCH₂CH₂CO₂CH₃ 532 N CH NHCHO Ph 123 CH CH NHCHO CH₂CH₂CH₂CO₂CH₃ 533 N CHNHCHO 2-furanyl 124 CH CH NHCHO cyclopropyl 534 N CH NHCHO 2-thiophenyl125 CH CH NHCHO CO₂CH₃ 535 N CH NHCHO OPh 126 CH CH NHCHO CO₂CH₂CH₃ 536N CH NHCHO OCH₂CCH 127 CH CH NHCHO Ph 537 N CH NHCHO OCH₂CH₂OCH₃ 128 CHCH NHCHO 2-furanyl 538 N CH NHCHO SCH₃ 129 CH CH NHCHO 2-thiophenyl 539N CH NHCHO SCH₂CH₃ 130 CH CH NHCHO OPh 540 N CH NHCHO SCH(CH₃)₂ 131 CHCH NHCHO OCH₂CCH 541 N CF Cl H 132 CH CH NHCHO OCH₂CH₂OCH₃ 542 N CF ClCH₃ 133 CH CH NHCHO SCH₃ 543 N CF Cl CH₂CH₃ 134 CH CH NHCHO SCH₂CH₃ 544N CF Cl OCH₃ 135 CH CH NHCHO SCH(CH₃)₂ 545 N CF Cl OCH₂CH₃ 136 CH CF ClH 546 N CF Cl CH₂OCH₃ 137 CH CF Cl CH₃ 547 N CF Cl CH(CH₃)OCH₃ 138 CH CFCl CH₂CH₃ 548 N CF Cl C(CH₃)₂OCH₃ 139 CH CF Cl OCH₃ 549 N CF Cl CH₂F 140CH CF Cl OCH₂CH₃ 550 N CF Cl CH₂Cl 141 CH CF Cl CH₂OCH₃ 551 N CF ClCH₂Br 142 CH CF Cl CH(CH₃)OCH₃ 552 N CF Cl CH₂CF₃ 143 CH CF ClC(CH₃)₂OCH₃ 553 N CF Cl CH₂CO₂CH₃ 144 CH CF Cl CH₂F 554 N CF ClCH₂CH₂CO₂CH₃ 145 CH CF Cl CH₂Cl 555 N CF Cl CH₂CH₂CH₂CO₂CH₃ 146 CH CF ClCH₂Br 556 N CF Cl cyclopropyl 147 CH CF Cl CH₂CF₃ 557 N CF Cl CO₂CH₃ 148CH CF Cl CH₂CO₂CH₃ 558 N CF Cl CO₂CH₂CH₃ 149 CH CF Cl CH₂CH₂CO₂CH₃ 559 NCF Cl Ph 150 CH CF Cl CH₂CH₂CH₂CO₂CH₃ 560 N CF Cl 2-furanyl 151 CH CF Clcyclopropyl 561 N CF Cl 2-thiophenyl 152 CH CF Cl CO₂CH₃ 562 N CF Cl OPh153 CH CF Cl CO₂CH₂CH₃ 563 N CF Cl OCH₂CCH 154 CH CF Cl Ph 564 N CF ClOCH₂CH₂OCH₃ 155 CH CF Cl 2-furanyl 565 N CF Cl SCH₃ 156 CH CF Cl2-thiophenyl 566 N CF Cl SCH₂CH₃ 157 CH CF Cl OPh 567 N CF Cl SCH(CH₃)₂158 CH CF Cl OCH₂CCH 568 N CF Br H 159 CH CF Cl OCH₂CH₂OCH₃ 569 N CF BrCH₃ 160 CH CF Cl SCH₃ 570 N CF Br CH₂CH₃ 161 CH CF Cl SCH₂CH₃ 571 N CFBr OCH₃ 162 CH CF Cl SCH(CH₃)₂ 572 N CF Br OCH₂CH₃ 163 CH CF Br H 573 NCF Br CH₂OCH₃ 164 CH CF Br CH₃ 574 N CF Br CH(CH₃)OCH₃ 165 CH CF BrCH₂CH₃ 575 N CF Br C(CH₃)₂OCH₃ 166 CH CF Br OCH₃ 576 N CF Br CH₂F 167 CHCF Br OCH₂CH₃ 577 N CF Br CH₂Cl 168 CH CF Br CH₂OCH₃ 578 N CF Br CH₂Br169 CH CF Br CH(CH₃)OCH₃ 579 N CF Br CH₂CF₃ 170 CH CF Br C(CH₃)₂OCH₃ 580N CF Br CH₂CO₂CH₃ 171 CH CF Br CH₂F 581 N CF Br CH₂CH₂CO₂CH₃ 172 CH CFBr CH₂Cl 582 N CF Br CH₂CH₂CH₂CO₂CH₃ 173 CH CF Br CH₂Br 583 N CF Brcyclopropyl 174 CH CF Br CH₂CF₃ 584 N CF Br CO₂CH₃ 175 CH CF BrCH₂CO₂CH₃ 585 N CF Br CO₂CH₂CH₃ 176 CH CF Br CH₂CH₂CO₂CH₃ 586 N CF Br Ph177 CH CF Br CH₂CH₂CH₂CO₂CH₃ 587 N CF Br 2-furanyl 178 CH CF Brcyclopropyl 588 N CF Br 2-thiophenyl 179 CH CF Br CO₂CH₃ 589 N CF Br OPh180 CH CF Br CO₂CH₂CH₃ 590 N CF Br OCH₂CCH 181 CH CF Br Ph 591 N CF BrOCH₂CH₂OCH₃ 182 CH CF Br 2-furanyl 592 N CF Br SCH₃ 183 CH CF Br2-thiophenyl 593 N CF Br SCH₂CH₃ 184 CH CF Br OPh 594 N CF Br SCH(CH₃)₂185 CH CF Br OCH₂CCH 595 N CF CH₃ H 186 CH CF Br OCH₂CH₂OCH₃ 596 N CFCH₃ CH₃ 187 CH CF Br SCH₃ 597 N CF CH₃ CH₂CH₃ 188 CH CF Br SCH₂CH₃ 598 NCF CH₃ OCH₃ 189 CH CF Br SCH(CH₃)₂ 599 N CF CH₃ OCH₂CH₃ 190 CH CF CH₃ H600 N CF CH₃ CH₂OCH₃ 191 CH CF CH₃ CH₃ 601 N CF CH₃ CH(CH₃)OCH₃ 192 CHCF CH₃ CH₂CH₃ 602 N CF CH₃ C(CH₃)₂OCH₃ 193 CH CF CH₃ OCH₃ 603 N CF CH₃CH₂F 194 CH CF CH₃ OCH₂CH₃ 604 N CF CH₃ CH₂Cl 195 CH CF CH₃ CH₂OCH₃ 605N CF CH₃ CH₂Br 196 CH CF CH₃ CH(CH₃)OCH₃ 606 N CF CH₃ CH₂CF₃ 197 CH CFCH₃ C(CH₃)₂OCH₃ 607 N CF CH₃ CH₂CO₂CH₃ 198 CH CF CH₃ CH₂F 608 N CF CH₃CH₂CH₂CO₂CH₃ 199 CH CF CH₃ CH₂Cl 609 N CF CH₃ CH₂CH₂CH₂CO₂CH₃ 200 CH CFCH₃ CH₂Br 610 N CF CH₃ cyclopropyl 201 CH CF CH₃ CH₂CF₃ 611 N CF CH₃CO₂CH₃ 202 CH CF CH₃ CH₂CO₂CH₃ 612 N CF CH₃ CO₂CH₂CH₃ 203 CH CF CH₃CH₂CH₂CO₂CH₃ 613 N CF CH₃ Ph 204 CH CF CH₃ CH₂CH₂CH₂CO₂CH₃ 614 N CF CH₃2-furanyl 205 CH CF CH₃ cyclopropyl 615 N CF CH₃ 2-thiophenyl 206 CH CFCH₃ CO₂CH₃ 616 N CF CH₃ OPh 207 CH CF CH₃ CO₂CH₂CH₃ 617 N CF CH₃ OCH₂CCH208 CH CF CH₃ Ph 618 N CF CH₃ OCH₂CH₂OCH₃ 209 CH CF CH₃ 2-furanyl 619 NCF CH₃ SCH₃ 210 CH CF CH₃ 2-thiophenyl 620 N CF CH₃ SCH₂CH₃ 211 CH CFCH₃ OPh 621 N CF CH₃ SCH(CH₃)₂ 212 CH CF CH₃ OCH₂CCH 622 N CF OCH₃ H 213CH CF CH₃ OCH₂CH₂OCH₃ 623 N CF OCH₃ CH₃ 214 CH CF CH₃ SCH₃ 624 N CF OCH₃CH₂CH₃ 215 CH CF CH₃ SCH₂CH₃ 625 N CF OCH₃ OCH₃ 216 CH CF CH₃ SCH(CH₃)₂626 N CF OCH₃ OCH₂CH₃ 217 CH CF OCH₃ H 627 N CF OCH₃ CH₂OCH₃ 218 CH CFOCH₃ CH₃ 628 N CF OCH₃ CH(CH₃)OCH₃ 219 CH CF OCH₃ CH₂CH₃ 629 N CF OCH₃C(CH₃)₂OCH₃ 220 CH CF OCH₃ OCH₃ 630 N CF OCH₃ CH₂F 221 CH CF OCH₃OCH₂CH₃ 631 N CF OCH₃ CH₂Cl 222 CH CF OCH₃ CH₂OCH₃ 632 N CF OCH₃ CH₂Br223 CH CF OCH₃ CH(CH₃)OCH₃ 633 N CF OCH₃ CH₂CF₃ 224 CH CF OCH₃C(CH₃)₂OCH₃ 634 N CF OCH₃ CH₂CO₂CH₃ 225 CH CF OCH₃ CH₂F 635 N CF OCH₃CH₂CH₂CO₂CH₃ 226 CH CF OCH₃ CH₂Cl 636 N CF OCH₃ CH₂CH₂CH₂CO₂CH₃ 227 CHCF OCH₃ CH₂Br 637 N CF OCH₃ cyclopropyl 228 CH CF OCH₃ CH₂CF₃ 638 N CFOCH₃ CO₂CH₃ 229 CH CF OCH₃ CH₂CO₂CH₃ 639 N CF OCH₃ CO₂CH₂CH₃ 230 CH CFOCH₃ CH₂CH₂CO₂CH₃ 640 N CF OCH₃ Ph 231 CH CF OCH₃ CH₂CH₂CH₂CO₂CH₃ 641 NCF OCH₃ 2-furanyl 232 CH CF OCH₃ cyclopropyl 642 N CF OCH₃ 2-thiophenyl233 CH CF OCH₃ CO₂CH₃ 643 N CF OCH₃ OPh 234 CH CF OCH₃ CO₂CH₂CH₃ 644 NCF OCH₃ OCH₂CCH 235 CH CF OCH₃ Ph 645 N CF OCH₃ OCH₂CH₂OCH₃ 236 CH CFOCH₃ 2-furanyl 646 N CF OCH₃ SCH₃ 237 CH CF OCH₃ 2-thiophenyl 647 N CFOCH₃ SCH₂CH₃ 238 CH CF OCH₃ OPh 648 N CF OCH₃ SCH(CH₃)₂ 239 CH CF OCH₃OCH₂CCH 649 N CF NHCHO H 240 CH CF OCH₃ OCH₂CH₂OCH₃ 650 N CF NHCHO CH₃241 CH CF OCH₃ SCH₃ 651 N CF NHCHO CH₂CH₃ 242 CH CF OCH₃ SCH₂CH₃ 652 NCF NHCHO OCH₃ 243 CH CF OCH₃ SCH(CH₃)₂ 653 N CF NHCHO OCH₂CH₃ 244 CH CFNHCHO H 654 N CF NHCHO CH₂OCH₃ 245 CH CF NHCHO CH₃ 655 N CF NHCHOCH(CH₃)OCH₃ 246 CH CF NHCHO CH₂CH₃ 656 N CF NHCHO C(CH₃)₂OCH₃ 247 CH CFNHCHO OCH₃ 657 N CF NHCHO CH₂F 248 CH CF NHCHO OCH₂CH₃ 658 N CF NHCHOCH₂Cl 249 CH CF NHCHO CH₂OCH₃ 659 N CF NHCHO CH₂Br 250 CH CF NHCHOCH(CH₃)OCH₃ 660 N CF NHCHO CH₂CF₃ 251 CH CF NHCHO C(CH₃)₂OCH₃ 661 N CFNHCHO CH₂CO₂CH₃ 252 CH CF NHCHO CH₂F 662 N CF NHCHO CH₂CH₂CO₂CH₃ 253 CHCF NHCHO CH₂Cl 663 N CF NHCHO CH₂CH₂CH₂CO₂CH₃ 254 CH CF NHCHO CH₂Br 664N CF NHCHO cyclopropyl 255 CH CF NHCHO CH₂CF₃ 665 N CF NHCHO CO₂CH₃ 256CH CF NHCHO CH₂CO₂CH₃ 666 N CF NHCHO CO₂CH₂CH₃ 257 CH CF NHCHOCH₂CH₂CO₂CH₃ 667 N CF NHCHO Ph 258 CH CF NHCHO CH₂CH₂CH₂CO₂CH₃ 668 N CFNHCHO 2-furanyl 259 CH CF NHCHO cyclopropyl 669 N CF NHCHO 2-thiophenyl260 CH CF NHCHO CO₂CH₃ 670 N CF NHCHO OPh 261 CH CF NHCHO CO₂CH₂CH₃ 671N CF NHCHO OCH₂CCH 262 CH CF NHCHO Ph 672 N CF NHCHO OCH₂CH₂OCH₃ 263 CHCF NHCHO 2-furanyl 673 N CF NHCHO SCH₃ 264 CH CF NHCHO 2-thiophenyl 674N CF NHCHO SCH₂CH₃ 265 CH CF NHCHO OPh 675 N CF NHCHO SCH(CH₃)₂ 266 CHCF NHCHO OCH₂CCH 676 N N Cl H 267 CH CF NHCHO OCH₂CH₂OCH₃ 677 N N Cl CH₃268 CH CF NHCHO SCH₃ 678 N N Cl CH₂CH₃ 269 CH CF NHCHO SCH₂CH₃ 679 N NCl OCH₃ 270 CH CF NHCHO SCH(CH₃)₂ 680 N N Cl OCH₂CH₃ 271 CH N Cl H 681 NN Cl CH₂OCH₃ 272 CH N Cl CH₃ 682 N N Cl CH(CH₃)OCH₃ 273 CH N Cl CH₂CH₃683 N N Cl C(CH₃)₂OCH₃ 274 CH N Cl OCH₃ 684 N N Cl CH₂F 275 CH N ClOCH₂CH₃ 685 N N Cl CH₂Cl 276 CH N Cl CH₂OCH₃ 686 N N Cl CH₂Br 277 CH NCl CH(CH₃)OCH₃ 687 N N Cl CH₂CF₃ 278 CH N Cl C(CH₃)₂OCH₃ 688 N N ClCH₂CO₂CH₃ 279 CH N Cl CH₂F 689 N N Cl CH₂CH₂CO₂CH₃ 280 CH N Cl CH₂Cl 690N N Cl CH₂CH₂CH₂CO₂CH₃ 281 CH N Cl CH₂Br 691 N N Cl cyclopropyl 282 CH NCl CH₂CF₃ 692 N N Cl CO₂CH₃ 283 CH N Cl CH₂CO₂CH₃ 693 N N Cl CO₂CH₂CH₃284 CH N Cl CH₂CH₂CO₂CH₃ 694 N N Cl Ph 285 CH N Cl CH₂CH₂CH₂CO₂CH₃ 695 NN Cl 2-furanyl 286 CH N Cl cyclopropyl 696 N N Cl 2-thiophenyl 287 CH NCl CO₂CH₃ 697 N N Cl OPh 288 CH N Cl CO₂CH₂CH₃ 698 N N Cl OCH₂CCH 289 CHN Cl Ph 699 N N Cl OCH₂CH₂OCH₃ 290 CH N Cl 2-furanyl 700 N N Cl SCH₃ 291CH N Cl 2-thiophenyl 701 N N Cl SCH₂CH₃ 292 CH N Cl OPh 702 N N ClSCH(CH₃)₂ 293 CH N Cl OCH₂CCH 703 N N Br H 294 CH N Cl OCH₂CH₂OCH₃ 704 NN Br CH₃ 295 CH N Cl SCH₃ 705 N N Br CH₂CH₃ 296 CH N Cl SCH₂CH₃ 706 N NBr OCH₃ 297 CH N Cl SCH(CH₃)₂ 707 N N Br OCH₂CH₃ 298 CH N Br H 708 N NBr CH₂OCH₃ 299 CH N Br CH₃ 709 N N Br CH(CH₃)OCH₃ 300 CH N Br CH₂CH₃ 710N N Br C(CH₃)₂OCH₃ 301 CH N Br OCH₃ 711 N N Br CH₂F 302 CH N Br OCH₂CH₃712 N N Br CH₂Cl 303 CH N Br CH₂OCH₃ 713 N N Br CH₂Br 304 CH N BrCH(CH₃)OCH₃ 714 N N Br CH₂CF₃ 305 CH N Br C(CH₃)₂OCH₃ 715 N N BrCH₂CO₂CH₃ 306 CH N Br CH₂F 716 N N Br CH₂CH₂CO₂CH₃ 307 CH N Br CH₂Cl 717N N Br CH₂CH₂CH₂CO₂CH₃ 308 CH N Br CH₂Br 718 N N Br cyclopropyl 309 CH NBr CH₂CF₃ 719 N N Br CO₂CH₃ 310 CH N Br CH₂CO₂CH₃ 720 N N Br CO₂CH₂CH₃311 CH N Br CH₂CH₂CO₂CH₃ 721 N N Br Ph 312 CH N Br CH₂CH₂CH₂CO₂CH₃ 722 NN Br 2-furanyl 313 CH N Br cyclopropyl 723 N N Br 2-thiophenyl 314 CH NBr CO₂CH₃ 724 N N Br OPh 315 CH N Br CO₂CH₂CH₃ 725 N N Br OCH₂CCH 316 CHN Br Ph 726 N N Br OCH₂CH₂OCH₃ 317 CH N Br 2-furanyl 727 N N Br SCH₃ 318CH N Br 2-thiophenyl 728 N N Br SCH₂CH₃ 319 CH N Br OPh 729 N N BrSCH(CH₃)₂ 320 CH N Br OCH₂CCH 730 N N CH₃ H 321 CH N Br OCH₂CH₂OCH₃ 731N N CH₃ CH₃ 322 CH N Br SCH₃ 732 N N CH₃ CH₂CH₃ 323 CH N Br SCH₂CH₃ 733N N CH₃ OCH₃ 324 CH N Br SCH(CH₃)₂ 734 N N CH₃ OCH₂CH₃ 325 CH N CH₃ H735 N N CH₃ CH₂OCH₃ 326 CH N CH₃ CH₃ 736 N N CH₃ CH(CH₃)OCH₃ 327 CH NCH₃ CH₂CH₃ 737 N N CH₃ C(CH₃)₂OCH₃ 328 CH N CH₃ OCH₃ 738 N N CH₃ CH₂F329 CH N CH₃ OCH₂CH₃ 739 N N CH₃ CH₂Cl 330 CH N CH₃ CH₂OCH₃ 740 N N CH₃CH₂Br 331 CH N CH₃ CH(CH₃)OCH₃ 741 N N CH₃ CH₂CF₃ 332 CH N CH₃C(CH₃)₂OCH₃ 742 N N CH₃ CH₂CO₂CH₃ 333 CH N CH₃ CH₂F 743 N N CH₃CH₂CH₂CO₂CH₃ 334 CH N CH₃ CH₂Cl 744 N N CH₃ CH₂CH₂CH₂CO₂CH₃ 335 CH N CH₃CH₂Br 745 N N CH₃ cyclopropyl 336 CH N CH₃ CH₂CF₃ 746 N N CH₃ CO₂CH₃ 337CH N CH₃ CH₂CO₂CH₃ 747 N N CH₃ CO₂CH₂CH₃ 338 CH N CH₃ CH₂CH₂CO₂CH₃ 748 NN CH₃ Ph 339 CH N CH₃ CH₂CH₂CH₂CO₂CH₃ 749 N N CH₃ 2-furanyl 340 CH N CH₃cyclopropyl 750 N N CH₃ 2-thiophenyl 341 CH N CH₃ CO₂CH₃ 751 N N CH₃ OPh342 CH N CH₃ CO₂CH₂CH₃ 752 N N CH₃ OCH₂CCH 343 CH N CH₃ Ph 753 N N CH₃OCH₂CH₂OCH₃ 344 CH N CH₃ 2-furanyl 754 N N CH₃ SCH₃ 345 CH N CH₃2-thiophenyl 755 N N CH₃ SCH₂CH₃ 346 CH N CH₃ OPh 756 N N CH₃ SCH(CH₃)₂347 CH N CH₃ OCH₂CCH 757 N N OCH₃ H 348 CH N CH₃ OCH₂CH₂OCH₃ 758 N NOCH₃ CH₃ 349 CH N CH₃ SCH₃ 759 N N OCH₃ CH₂CH₃ 350 CH N CH₃ SCH₂CH₃ 760N N OCH₃ OCH₃ 351 CH N CH₃ SCH(CH₃)₂ 761 N N OCH₃ OCH₂CH₃ 352 CH N OCH₃H 762 N N OCH₃ CH₂OCH₃ 353 CH N OCH₃ CH₃ 763 N N OCH₃ CH(CH₃)OCH₃ 354 CHN OCH₃ CH₂CH₃ 764 N N OCH₃ C(CH₃)₂OCH₃ 355 CH N OCH₃ OCH₃ 765 N N OCH₃CH₂F 356 CH N OCH₃ OCH₂CH₃ 766 N N OCH₃ CH₂Cl 357 CH N OCH₃ CH₂OCH₃ 767N N OCH₃ CH₂Br 358 CH N OCH₃ CH(CH₃)OCH₃ 768 N N OCH₃ CH₂CF₃ 359 CH NOCH₃ C(CH₃)₂OCH₃ 769 N N OCH₃ CH₂CO₂CH₃ 360 CH N OCH₃ CH₂F 770 N N OCH₃CH₂CH₂CO₂CH₃ 361 CH N OCH₃ CH₂Cl 771 N N OCH₃ CH₂CH₂CH₂CO₂CH₃ 362 CH NOCH₃ CH₂Br 772 N N OCH₃ cyclopropyl 363 CH N OCH₃ CH₂CF₃ 773 N N OCH₃CO₂CH₃ 364 CH N OCH₃ CH₂CO₂CH₃ 774 N N OCH₃ CO₂CH₂CH₃ 365 CH N OCH₃CH₂CH₂CO₂CH₃ 775 N N OCH₃ Ph 366 CH N OCH₃ CH₂CH₂CH₂CO₂CH₃ 776 N N OCH₃2-furanyl 367 CH N OCH₃ cyclopropyl 777 N N OCH₃ 2-thiophenyl 368 CH NOCH₃ CO₂CH₃ 778 N N OCH₃ OPh 369 CH N OCH₃ CO₂CH₂CH₃ 779 N N OCH₃OCH₂CCH 370 CH N OCH₃ Ph 780 N N OCH₃ OCH₂CH₂OCH₃ 371 CH N OCH₃2-furanyl 781 N N OCH₃ SCH₃ 372 CH N OCH₃ 2-thiophenyl 782 N N OCH₃SCH₂CH₃ 373 CH N OCH₃ OPh 783 N N OCH₃ SCH(CH₃)₂ 374 CH N OCH₃ OCH₂CCH784 N N NHCHO H 375 CH N OCH₃ OCH₂CH₂OCH₃ 785 N N NHCHO CH₃ 376 CH NOCH₃ SCH₃ 786 N N NHCHO CH₂CH₃ 377 CH N OCH₃ SCH₂CH₃ 787 N N NHCHO OCH₃378 CH N OCH₃ SCH(CH₃)₂ 788 N N NHCHO OCH₂CH₃ 379 CH N NHCHO H 789 N NNHCHO CH₂OCH₃ 380 CH N NHCHO CH₃ 790 N N NHCHO CH(CH₃)OCH₃ 381 CH NNHCHO CH₂CH₃ 791 N N NHCHO C(CH₃)₂OCH₃ 382 CH N NHCHO OCH₃ 792 N N NHCHOCH₂F 383 CH N NHCHO OCH₂CH₃ 793 N N NHCHO CH₂Cl 384 CH N NHCHO CH₂OCH₃794 N N NHCHO CH₂Br 385 CH N NHCHO CH(CH₃)OCH₃ 795 N N NHCHO CH₂CF₃ 386CH N NHCHO C(CH₃)₂OCH₃ 796 N N NHCHO CH₂CO₂CH₃ 387 CH N NHCHO CH₂F 797 NN NHCHO CH₂CH₂CO₂CH₃ 388 CH N NHCHO CH₂Cl 798 N N NHCHO CH₂CH₂CH₂CO₂CH₃389 CH N NHCHO CH₂Br 799 N N NHCHO cyclopropyl 390 CH N NHCHO CH₂CF₃ 800N N NHCHO CO₂CH₃ 391 CH N NHCHO CH₂CO₂CH₃ 801 N N NHCHO CO₂CH₂CH₃ 392 CHN NHCHO CH₂CH₂CO₂CH₃ 802 N N NHCHO Ph 393 CH N NHCHO CH₂CH₂CH₂CO₂CH₃ 803N N NHCHO 2-furanyl 394 CH N NHCHO cyclopropyl 804 N N NHCHO2-thiophenyl 395 CH N NHCHO CO₂CH₃ 805 N N NHCHO OPh 396 CH N NHCHOCO₂CH₂CH₃ 806 N N NHCHO OCH₂CCH 397 CH N NHCHO Ph 807 N N NHCHOOCH₂CH₂OCH₃ 398 CH N NHCHO 2-furanyl 808 N N NHCHO SCH₃ 399 CH N NHCHO2-thiophenyl 809 N N NHCHO SCH₂CH₃ 400 CH N NHCHO OPh 810 N N NHCHOSCH(CH₃)₂ 401 CH N NHCHO OCH₂CCH 811 N CF CH₃ CH(CH₃)OCO₂CH₃ 402 CH NNHCHO OCH₂CH₂OCH₃ 812 N CF CH₃ CH(CH₃)OCO₂CH₂CH₃ 403 CH N NHCHO SCH₃ 813N CF CH₃ CH(CH₃)OC(O)CH₃ 404 CH N NHCHO SCH₂CH₃ 814 N CF CH₃ CH(CH₃)0H405 CH N NHCHO SCH(CH₃)₂ 815 N CF CH₃ CH₂OCH₂CH₃ 406 N CH Cl H 816 N CFCH₃ CH₂OC(O)CH₃ 407 N CH Cl CH₃ 817 N CF CH₃ CH₂(C₆H₅) 408 N CH ClCH₂CH₃ 818 N CF CH₃ CH₂OCH₂(C₆H₃) 409 N CH Cl OCH₃ 819 N CF CH₃CH(CH₃)OCH₂(C₆H₅) 410 N CH Cl OCH₂CH₃ 820 N CF CH₃ N(CH₂CH₃)₂wherein

-   a) 820 compounds of formula (I.a):

wherein R¹, R², X and Y are as defined in Table 1.

-   b) 820 compounds of formula (I.b):

wherein R¹, R², X and Y are as defined in Table 1.

-   c) 820 compounds of formula (I.c):

wherein R¹, R², X and Y are as defined in Table 1.

Formulation Examples

Wettable powders a) b) c) active ingredient [compound of formula (I)]25% 50 % 75% sodium lignosulfonate  5%  5% — sodium lauryl sulfate  3% — 5% sodium diisobutylnaphthalenesulfonate —  6% 10% phenol polyethyleneglycol ether —  2% — (7 - 8 mol of ethylene oxide) highly dispersedsilicic acid  5% 10% 10% Kaolin 62% 27% —

The active ingredient is thoroughly mixed with the adjuvants and themixture is thoroughly ground in a suitable mill, affording wettablepowders that can be diluted with water to give suspensions of thedesired concentration.

Powders for dry seed treatment a) b) c) active ingredient [compound offormula (I)] 25% 50% 75% light mineral oil  5%  5%  5% highly dispersedsilicic acid  5%  5% — Kaolin 65% 40% — Talcum — 20%The active ingredient is thoroughly mixed with the adjuvants and themixture is thoroughly ground in a suitable mill, affording powders thatcan be used directly for seed treatment.

Emulsifiable concentrate active ingredient [compound of formula (I)] 10%octylphenol polyethylene glycol ether  3% (4 - 5 mol of ethylene oxide)calcium dodecylbenzenesulfonate  3% castor oil polyglycol ether (35 molof ethylene oxide)  4% Cyclohexanone 30% xylene mixture 50%

Emulsions of any required dilution, which can be used in plantprotection, can be obtained from this concentrate by dilution withwater.

Dusts a) b) c) Active ingredient [compound of formula (I)]  5%  6%  4%talcum 95% — — Kaolin — 94% — mineral filler — — 96%Ready-for-use dusts are obtained by mixing the active ingredient withthe carrier and grinding the mixture in a suitable mill. Such powderscan also be used for dry dressings for seed.

Extruder granules Active ingredient [compound of formula (I)] 15% sodiumlignosulfonate  2% carboxymethylcellulose  1% Kaolin 82%The active ingredient is mixed and ground with the adjuvants, and themixture is moistened with water. The mixture is extruded and then driedin a stream of air.

Coated granules Active ingredient [compound of formula (I)]  8%polyethylene glycol (mol. wt. 200)  3% Kaolin 89%The finely ground active ingredient is uniformly applied, in a mixer, tothe kaolin moistened with polyethylene glycol. Non-dusty coated granulesare obtained in this manner.

Suspension concentrate active ingredient [compound of formula (I)] 40%propylene glycol 10% nonylphenol polyethylene glycol ether (15 mol ofethylene oxide)  6% Sodium lignosulfonate 10% carboxymethylcellulose  1%silicone oil (in the form of a 75% emulsion in water)  1% Water 32%The finely ground active ingredient is intimately mixed with theadjuvants, giving a suspension concentrate from which suspensions of anydesired dilution can be obtained by dilution with water. Using suchdilutions, living plants as well as plant propagation material can betreated and protected against infestation by microorganisms, byspraying, pouring or immersion.

Flowable concentrate for seed treatment active ingredient [compound offormula (I)]   40% propylene glycol    5% copolymer butanol PO/EO    2%tristyrenephenole with 10 - 20 moles EO    2% 1,2-benzisothiazolin-3-one 0.5% (in the form of a 20% solution in water) monoazo-pigment calciumsalt    5% Silicone oil (in the form of a 75% emulsion in water)  0.2%Water 45.3%The finely ground active ingredient is intimately mixed with theadjuvants, giving a suspension concentrate from which suspensions of anydesired dilution can be obtained by dilution with water. Using suchdilutions, living plants as well as plant propagation material can betreated and protected against infestation by microorganisms, byspraying, pouring or immersion.

Slow Release Capsule Suspension

-   28 parts of a combination of the compound of formula (I) are mixed    with 2 parts of an aromatic solvent and 7 parts of toluene    diisocyanate/polymethylene-polyphenylisocyanate-mixture (8:1). This    mixture is emulsified in a mixture of 1.2 parts of polyvinyl    alcohol, 0.05 parts of a defoamer and 51.6 parts of water until the    desired particle size is achieved. To this emulsion a mixture of 2.8    parts 1,6-diaminohexane in 5.3 parts of water is added. The mixture    is agitated until the polymerization reaction is completed.

The obtained capsule suspension is stabilized by adding 0.25 parts of athickener and 3 parts of a dispersing agent. The capsule suspensionformulation contains 28% of the active ingredients. The medium capsulediameter is 8-microns.

The resulting formulation is applied to seeds as an aqueous suspensionin an apparatus suitable for that purpose.

EXAMPLES

The Examples which follow serve to illustrate the invention. Thecompounds of the invention can be distinguished from known compounds byvirtue of greater efficacy at low application rates, which can beverified by the person skilled in the art using the experimentalprocedures outlined in the Examples, using lower application rates ifnecessary, for example 50 ppm, 12.5 ppm, 6 ppm, 3 ppm, 1.5 ppm, 0.8 ppmor 0.2 ppm.

Compounds of formula (I) may possess any number of benefits including,inter alia, advantageous levels of biological activity for protectingplants against diseases that are caused by fungi or superior propertiesfor use as agrochemical active ingredients (for example, greaterbiological activity, an advantageous spectrum of activity, an increasedsafety profile (including improved crop tolerance), improvedphysico-chemical properties, or increased biodegradability).

LIST OF ABBREVIATIONS

-   ° C.=degrees Celsius

CDCI₃=chloroform-d

-   d=doublet-   Pd₂(dba)₃=Tris(dibenzylideneacetone)dipalladium(0)-   DIPEA=N,N-diisopropylethylamine-   DMF=dimethylformamide-   HATU=1-[Bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium    3-oxid hexafluorophosphate-   m=multiplet-   MHz=mega hertz-   mp=melting point-   N=normal-   ppm=parts per million-   q=quartet-   s=singlet-   t=triplet-   THF=tetrahydrofuran-   Xantphos=4,5-Bis(diphenylphosphino)-9,9-dimethylxanthene

Example 1 This example illustrates the preparation of2-[acetyl-(2,6-difluoro-4-pyridyl)amino]-N-(2,2-dimethylcyclobutyl)-5-methyl-thiazole-4-carboxamide(Compound I.b.596)

a) Preparation of methyl2-[(2,6-difluoro-4-pyridyl)amino]-5-methyl-thiazole-4-carboxylate

Under Argon atmosphere, Xantphos (0.2 equiv.), Pd2(dba)₃ (0.1 equiv.)and cesium carbonate (2 equiv.) were added to a degassed, stirredmixture of methyl 2-bromo-5-methyl-thiazole-4-carboxylate (4.6 g, 18.5mmol, 1 equiv.) and 2,6-difluoropyridin-4-amine (1 equiv.) in1,4-dioxane (660 mL). The reaction was heated to reflux and stirred for4 h before allowing the temperature to cool to room temperature. Themixture was diluted with ethyl acetate and filtered over Celite, and theresulting filtrate was concentrated using a rotatory evaporator.Purification by column chromatography on silica gel (eluent mixturescyclohexane/ethyl acetate) afforded the desired methyl2-[(2,6-difluoro-4-pyridyl)amino]-5-methyl-thiazole-4-carboxylate (1.8g, 6.31 mmol). ¹H-NMR (400 MHz, CDCI3): 6=2.73 (s, 3H), 3.94 (s, 3H),6.75 (s, 1H).

b) Preparation of2-[(2,6-difluoro-4-pyridyl)amino]-5-methyl-thiazole-4-carboxylic acid

Lithium hydroxide monohydrate (4 equiv.) was added to a solution of2-[(2,6-difluoro-4-pyridyl)amino]-5-methyl-thiazole-4-carboxylic acid(1.8 g, 6.31 mmol) in a mixture of tetrahydrofuran (mL) and water (12mL). The reaction mixture was stirred 16 h at room temperature, then thesolvents were removed in vacuo. The residue was diluted with ethylacetate and water, then 2 N hydrochloric acid was slowly added until apH of 3-4 was reached. The formed precipitate was isolated by filtrationand washed twice with water, giving the desired product2-[(2,6-difluoro-4-pyridyl)amino]-5-methyl-thiazole-4-carboxylic acid(1.55 g, 5.71 mmol). ¹H-NMR (400 MHz, (CD3)₂S0): 6 =2.69 (s, 3H), 7.30(s, 2H), 11.35 (bs, 1H), 12.90 (bs, 1H).

-   c) Preparation of    2-[(2,6-difluoro-4-pyridyl)amino]-N-(2,2-dimethylcyclobutyI)-5-methyl-thiazole-4-carboxamide

(2,2-dimethylcyclobutyl) ammonium chloride (1.1 equiv.), HATU (1.1.equiv.), and DIP{EA (2.6 equiv.), were added in sequence to a DMFsolution (9.2 mL) of2-[(2,6-difluoro-4-pyridyl)amino]-5-methyl-thiazole-4-carboxylic acid(250 mg, 0.92 mmol, 1 equiv.). The resulting solution was stirred atroom temperature for 1 h until consumption of starting material (LCMScontrol). Then a saturated NaHCO₃ solution was added to the mixture andthe solution extracted three times with ethyl acetate. The organicphases were combined, dried over sodium sulphate and the volatilesremoved by rotatory evaporator. Purification by column chromatography onsilica gel (eluent: mixtures of cyclohexane/ethyl acetate) gave thedesired product2-[(2,6-difluoro-4-pyridyl)amino]-N-(2,2-dimethylcyclobutyI)-5-methyl-thiazole-4-carboxamide(280 mg, 86% yield). ¹H-NMR (400 MHz, CDCI3): d =1.17 (s, 3H), 1.20 (s,3H), 1.50-1.75 (m, 2H), 1.86-1.92 (m, 1H), 2.29-2.36 (m, 1H), 2.79 (s,3H), 4.25-4.31 (m, 1H), 6.87 (s, 2H), 7.32 (d, 1H), 7.67 (s, 1H).

-   d)    2-[acetyl-(2,6-difluoro-4-pyridyl)amino]-N-(2,2-dimethylcyclobutyI)-5-methyl-thiazole-4-carboxamide    (Compound I.b.596)

A mixture of2-[(2,6-difluoro-4-pyridyl)amino]-N-(2,2-dimethylcyclobutyI)-5-methyl-thiazole-4-carboxamide(1.9 g, 5.4 mmol) in acetyl chloride (ml) was stirred under reflux for 3days. The reaction was then allowed to cool to room temperature and thevolatiles removed by rotatory evaporator. Purification of the crudematerial obtained by column chromatography on silica gel (eluent:mixtures of cyclohexane/ethyl acetate) gave the desired product2-[acetyl-(2,6-difluoro-4-pyridyl)amino]-N-(2,2-dimethylcyclobutyl)-5-methyl-thiazole-4-carboxamide(1.57 g, 3.98 mmol, 74% yield). ¹H-NMR (400 MHz, CDCI3): d =0.92 (s,3H), 1.12 (s, 3H), 1.48-1.75 (m, 3H), 2.10-2.30 (m, 1H), 2.17 (s, 3H),2.79 (s, 3H), 4.25-4.31 (m, 1H), 6.87 (s, 2H), 7.32 (d, 1 H).

Throughout this description, temperatures are given in degrees Celsius(° C.) and “m.p.” means melting point. LC/MS means Liquid ChromatographyMass Spectrometry and the description of the apparatus and the methodis:

-   Method A: ACQUITY UPLC from Waters, Waters UPLC HSS T3, 1.8 um    particle size, 30×2.1 mm column, 0.85 mL/min., 60° C., H₂O/MeOH    95:5+0.05% HCOOH (90%)/CH₃CN+0.05% HCOOH (10%)−1.2 min. —CH₃CN+0.05%    HCOOH (100%) −0.30 min., ACQUITY SQD Mass Spectrometer from Waters,    ionization method: electrospray (ESI), Polarity: positive ions,    Capillary (kV) 3.00, Cone (V) 30.00, Extractor (V) 2.00, Source    Temperature (° C.) 150, Desolvation Temperature (° C.) 350, Cone Gas    Flow (L/Hr) 0, Desolvation Gas Flow (L/Hr) 650).-   Method B: ACQUITY UPLC from Waters, Waters UPLC HSS T3, 1.8 μm    particle size, ×2.1 mm column, 0.85 mL/min., 60° C., H₂O/MeOH    95:5+0.05% HCOOH (90%)/CH₃CN+0.05% HCOOH (10%) −2.7 min.    —CH₃CN+0.05% HCOOH (100%) −0.30 min., ACQUITY SQD Mass Spectrometer    from Waters, ionization method: electrospray (ESI), Polarity:    positive ions, Capillary (kV) 3.00, Cone (V) 30.00, Extractor (V)    2.00, Source Temperature (° C.) 150, Desolvation Temperature (° C.)    350, Cone Gas Flow (L/Hr) 0, Desolvation Gas Flow (L/Hr) 650)).-   Method C: MS: ZQ Mass Spectrometer from Waters (Single quadrupole    mass spectrometer) Instrument Parameter: Ionisation method:    Electrospray Polarity: positive (negative) ions Capillary (kV) 30    3.00, Cone (V) 30.00, Extractor (V) 2.00, Gas Temperature (° C.)    350, Drying Gas Flow (mL/min)_(9.8), Neb press 45 psig, Mass range:    90 to 1000 Da. HPLC: HP 1100 HPLC from Agilent: solvent degasser,    quaternary pump (ZCQ)/binary pump (ZDQ), heated column compartment    and diode-array detector. Column: porpshell 120 C18, 2.7 μm particle    size, 120 Angström, 4.6×50 mm, Temp: ° C. DAD Wavelength range (nm):    190 to 400 Solvent Gradient:. A =water+0.1% HCOOH.    B=Acetonitrile+0.08% HCOOH. Mobile phase:

Flow Time (min) A% B% (ml/min) 0 85 15 0.6 4 5 95 0.6 10 5 95 0.6

-   Method D: Mass Spectrometer as method C.-   HPLC: Shimadzu LC-20A. Column: Dikma, DiamonsilCl₈(2) (5 μm,150*4.6    mm).

Mobile phase A: H₂O (add 0.1%TFA); Mobile phase B: ACN (add 0.1%TFA).Flow: 1.0 ml/min. Detection:UV©254 nm. Oven Temperature: ° C. MobilePhase:

Time (mins) A% B% 0 90 10 15 0 100 25 0 100 27 90 10 35 90 10

TABLE 2 Melting point and LC/MS data (R_(t) = Retention time) forselected compounds of Table 1. Mp No. Compound Name Structure (° C.)LC/MS I.c.813 [2-[(2,6-difluoro-4-pyridyl)-[5-methyl-4-(spiro[3.4]octan- 3-ylcarbamoyl)thiazol-2-yl]amino]-1-methyl-2-oxo- ethyl]acetate

R_(t) = 5.10 min (C); MS: m/z = 493 (M + 1) I.a.812[2-[[4-(cyclobutylcarbamoyl)- 5-methyl-thiazol-2-yl]-(2,6-difluoro-4-pyridyl)amino]-1- methyl-2-oxo-ethyl]ethyl carbonate

105-106 R_(t) = 15.33 min (D); MS: m/z = 469 (M + 1) I.c.811[2-[(2,6-difluoro-4-pyridyl)- [5-methyl-4-(spiro[3.4]octan-3-ylcarbamoyl)thiazol-2- yl]amino]-1-methyl-2-oxo- ethyl]methylcarbonate

R_(t) = 5.18 min (C); MS: m/z = 509 (M + 1) I.c.812[2-[(2,6-difluoro-4-pyridyl)- [5-methyl-4-(spiro[3.4]octan-3-ylcarbamoyl)thiazol-2- yl]amino]-1-methyl-2-oxo- ethyl]ethyl carbonate

106-108 R_(t) = 5.41 min (C); MS: m/z = 523 (M + 1) I.c.8142-[(2,6-difluoro-4-pyridyl)-(2- hydroxypropanoyl)amino]-5-methyl-N-spiro[3.4]octan-3- yl-thiazole-4-carboxamide

101-103 R_(t) = 5.15 min (C); MS: m/z = 451 (M + 1) I.a.8192-[2-benzyloxypropanoyl- (2,6-difluoro-4- pyridyl)amino]-N-cyclobutyl-5-methyl-thiazole-4- carboxamide

 98-100 R_(t) = 5.10 min (C); MS: m/z = 497 (M + 1) I.a.601N-cyclobutyl-2-[(2,6-difluoro- 4-pyridyl)-(2- methoxypropanoyl)amino]-5-methyl-thiazole-4- carboxamide

128-130 R_(t) = 13.80 min (D); MS: m/z = 411 (M + 1) I.b.816[2-[(2,6-difluoro-4-pyridyl)- [4-[(2,2- dimethylcyclobutyl)carbamoyl]-5-methyl-thiazol-2- yl]amino]-2-oxo-ethyl] acetate

65.5-67.2 R_(t) = 1.10 min (A); MS: m/z = 453 (M + 1) I.b.8172-[(2,6-difluoro-4-pyridyl)-(2- phenylacetyl)amino]-N-(2,2-dimethylcyclobutyl)-5- methyl-thiazole-4- carboxamide

R_(t) = 1.23 min (A); MS: m/z = 471 (M + 1) I.c.5962-[acetyl-(2,6-difluoro-4- pyridyl)amino]-5-methoxy-N-spiro[3.4]octan-3-yl-thiazole- 4-carboxamide

199-200 R_(t) = 1.06 min (A); MS: m/z = 437 (M + 1) I.c.6002-[(2,6-difluoro-4-pyridyl)-(2- methoxyacetyl)amino]-5-methyl-N-spiro[3.4]octan-3- yl-thiazole-4-carboxamide

R_(t) = 15.94 min (D); MS: m/z = 451 (M + 1) I.a.600N-cyclobutyl-2-[(2,6-difluoro- 4-pyridyl)-(2- methoxyacetyl)amino]-5-methyl-thiazole-4- carboxamide

R_(t) = 13.64 min (D); MS: m/z = 398 (M + 1) I.a.5962-[acetyl-(2,6-difluoro-4- pyridyl)amino]-N-cyclobutyl-5-methyl-thiazole-4- carboxamide

174-175 R_(t) = 13.92 min (D); MS: m/z = 367 (M + 1) I.b.8182-[(2-benzyloxyacetyl)-(2,6- difluoro-4-pyridyl)amino]-N-(2,2-dimethylcyclobutyl)-5- methyl-thiazole-4- carboxamide

182.9-187.1 R_(t) = 1.22 min (A); MS: m/z = 501 (M + 1) I.b.8152-[(2,6-difluoro-4-pyridyl)-(2- ethoxyacetyl)amino]-N-(2,2-dimethylcyclobutyl)-5- methyl-thiazole-4- carboxamide

146.1-147.6 R_(t) = 1.14 min (A); MS: m/z = 439 (M + 1) I.b.8202-[diethylcarbamoyl-(2,6- difluoro-4-pyridyl)amino]-N-(2,2-dimethylcyclobutyl)-5- methyl-thiazole-4- carboxamide

R_(t) = 1.19 min (A); MS: m/z = 452 (M + 1) I.b.6042-[(2-chloroacetyl)-(2,6- difluoro-4-pyridyl)amino]-N-(2,2-dimethylcyclobutyl)-5- methyl-thiazole-4- carboxamide

155.6-157.1 R_(t) = 1.11 min (A); MS: m/z = 429/431 (M + 1) I.b.607methyl 3-[(2,6-difluoro-4- pyridyl)-[4-[(2,2-dimethylcyclobutyl)carbamoyl]-5- methyl-thiazol-2-yl]amino]-3- oxo-propanoate

R_(t) = 1.09 min (A); MS: m/z = 453 (M + 1) I.b.6142-[(2,6-difluoro-4-pyridyl)- (furan-2-carbonyl)amino]-N- (2,2-dimethylcyclobutyl)-5- methyl-thiazole-4- carboxamide

166-172 R_(t) = 1.15 min (A); MS: m/z = 447 (M + 1) I.b.609 methyl5-[(2,6-difluoro-4- pyridyl)-[4-[(2,2-dimethyl cyclobutyl)carbamoyl]-5-methyl-thiazol-2-yl]amino]- 5-oxo-pentanoate

175-178 R_(t) = 1.12 min (A); MS: m/z = 481 (M + 1) I.b.6062-[(2,6-difluoro-4-pyridyl)- (3,3,3- trifluoropropanoyl)amino]-N-(2,2-dimethyl cyclobutyl)-5- methyl-thiazole-4- carboxamide

157-163 R_(t) = 1.15 min (A); MS: m/z = 463 (M + 1) I.b.621 S-isopropylN-(2,6-difluoro- 4-pyridyl)-N-[4-[(2,2- dimethylcyclobutyl)carbamoyl]-5- methyl-thiazol-2- yl]carbamothioate

155-158 R_(t) = 1.28 min (A); MS: m/z = 455 (M + 1) I.b.608 methyl4-[(2,6-difluoro-4- pyridyl)-[4-[(2,2-dimethyl cyclobutyl)carbamoyl]-5-methyl-thiazol-2-yl]amino]-4- oxo-butanoate

160-163 R_(t) = 1.11 min (A); MS: m/z = 467 (M + 1) I.b.6102-[cyclopropane carbonyl- (2,6-difluoro-4- pyridyl)amino]-N-(2,2-dimethyl cyclobutyl)-5- methyl-thiazole-4- carboxamide

165-170 R_(t) = 1.16 min (A); MS: m/z = 421 (M + 1) I.b.617 prop-2-ynylN-(2,6-difluoro- 4-pyridyl)-N-[4-[(2,2- dimethylcyclobutyl)carbamoyl]-5- methyl-thiazol-2- yl]carbamate

129-131 R_(t) = 1.14 min (A); MS: m/z = 435 (M + 1) I.b.616 phenylN-(2,6-difluoro-4- pyridyl)-N-[4-[(2,2- dimethylcyclobutyl)carbamoyl]-5-methyl-thiazol-2- yl]carbamate

138-140 R_(t) = 1.23 min (A); MS: m/z = 473 (M + 1) I.b.6032-[(2,6-difluoro-4-pyridyl)-(2- fluoroacetyl)amino]-N-(2,2- dimethylcyclobutyl)-5- methyl-thiazole-4- carboxamide

158-162 R_(t) = 1.09 min (A); MS: m/z = 413 (M + 1) I.b.6182-methoxyethyl N-(2,6- difluoro-4-pyridyl)-N-[4-[(2,2-dimethylcyclobutyl)carbamoyl]- 5-methyl-thiazol-2- yl]carbamate

R_(t) = 1.14 min (A); MS: m/z = 455 (M + 1) I.b.6002-[(2,6-difluoro-4-pyridyl)-(2- methoxyacetyl)amino]-N- (2,2-dimethylcyclobutyl)-5- methyl-thiazole-4- carboxamide

102-108 R_(t) = 1.08 min (A); MS: m/z = 425 (M + 1) I.b.599 ethylN-(2,6-difluoro-4- pyridyl)-N-[4-[(2,2- dimethylcyclobutyl)carbamoyl]-5-methyl-thiazol-2- yl]carbamate

R_(t) = 1.16 min (A); MS: m/z = 425 (M + 1) I.b.6152-[(2,6-difluoro-4-pyridyl)- (thiophene-2- carbonyl)amino]-N-(2,2-dimethyl cyclobutyl)-5- methyl-thiazole-4- carboxamide

178-185 R_(t) = 1.19 min (A); MS: m/z = 463 (M + 1) I.b.598 methylN-(2,6-difluoro-4- pyridyl)-N-[4-[(2,2- dimethylcyclobutyl)carbamoyl]-5-methyl-thiazol-2- yl]carbamate

R_(t) = 1.14 min (A); MS: m/z = 411 (M + 1) I.b.5952-[(2,6-difluoro-4-pyridyl)- formyl-amino]-N-(2,2- dimethylcyclobutyl)-5- methyl-thiazole-4- carboxamide

132-135 R_(t) = 1.09 min (A); MS: m/z = 381 (M + 1) I.b.612 ethyl2-[(2,6-difluoro-4- pyridyl)-[4-[(2,2- dimethylcyclobutyl)carbamoyl]-5-methyl-thiazol-2- yl]amino]-2-oxo-acetate

159-161 R_(t) = 1.17 min (A); MS: m/z = 453 (M + 1) I.b.6132-[benzoyl-(2,6-difluoro-4- pyridyl)amino]-N-(2,2-dimethylcyclobutyl)-5- methyl-thiazole-4- carboxamide

142-151 R_(t) = 1.19 min (A); MS: m/z = 457 (M + 1) I.b.5962-[acetyl-(2,6-difluoro-4- pyridyl)amino]-N-(2,2- dimethylcyclobutyl)-5- methyl-thiazole-4- carboxamide

141-145 R_(t) = 1.09 min (A); MS: m/z = 395 (M + 1) I.c.5962-[acetyl-(2,6-difluoro-4- pyridyl)amino]-5-methyl-N-spiro[3.4]octan-3-yl- thiazole-4-carboxamide

R_(t) = 1.15 min (A); MS: m/z = 421 (M + 1)

Surprisingly, it has been found that that the novel compounds of formula(I) i.e. wherein R¹ is hydrogen, C₁-C₆alkyl, C₁-C₆alkoxy,C₁-C₆haloalkyl, C₁-C₆alkoxyC₁-C₆alkyl, C₃-C₆cycloalkyl,C₁-C₆alkoxyC₁-C₃alkoxy, C₁-C₆alkoxycarbonyl,C₁-C₆alkoxycarbonylC₁-C₄alkyl, C₂-C₆alkenyloxy, C₂-C₆alkynyloxy,C₁-C₆alkylsulfanyl, phenyl, phenoxy, or heteroaryl, wherein theheteroaryl is a 5- or 6-membered aromatic monocyclic ring comprising 1or 2 heteroatoms individually selected from nitrogen, oxygen and sulfur,may show improved solubility (in particular in non-polar solvents)and/or photostability properties when compared to their correspondingfree amine, which are known from WO 2017/207362.

Throughout the following description, LogP means logarithm of thepartition coefficient, ppm means parts per million, and T50 representsthe half-time of the compound under irradiation conditions.

The methods used for these measurements are presented below.

Partition Coefficient

Octanol-water partition coefficients (presented as LogP) were measuredby an HPLC method using reverse phase mini-columns coated with octanol.The partition coefficient P is directly proportional to the HPLCretention factor. The general principles of this method have beendescribed for example in J. Pharm. Sci., 67 (1978) 1364-7.

A Waters HPLC system (model 1525 binary pump; 2707 autosampler withthermostat and model 2298 photodiode array detector) was used withHichrom mini-columns and an aqueous mobile phase containing 20 mMphosphate buffers adjusted to pH₇, saturated with 1-octanol (Aldrich,HPLC grade). Mini-columns used were HiRPB stationary phase, either 4.6mm internal diameter by 4 mm length or 2 mm internal diameter×10 mmlength. Anisole (Aldrich, 99%+purity, LogP 2.11) was used as the primaryreference to calibrate the system.

Photostability

Photostability tests were carried out by irradiation of thin-filmdeposits of compounds and formulations on glass surfaces, using afiltered xenon lamp system (Atlas Suntest) which reproduces the spectrumand intensity of sunlight. The spectral output power of the Suntest wasset to 750W/m2, which is the typical daily maximum irradiance level atnoon (UK, midsummer).

Test compounds were typically dissolved in HPLC grade methanol to give 1g/L stock solutions. Alternatively, formulated compounds were suspendedin water at the same concentration. 2pL droplets of test solutions werespotted onto microscope cover slips in a 3D printed holder, allowed todry then irradiated in the Suntest for varying times. Cover slips werethen removed from the Suntest and placed in 4 dram vials; 1 mL of washsolvent (typically 30:70 acetonitrile: 0.2% aqueous formic acid) wasadded, and the vials shaken to extract compounds into solution.Solutions were analysed by reverse phase HPLC, typically using a WatersUPLC system with Photodiode Array (PDA) and Waters columns (BEH C18,100×2.1 mm×1.7pm) using mixed aqueous:acetonitrile mobile phase,acidifed with 0.2% formic acid. Peak detection was at the optimumwavelength for each candidate compound and PDA peak areas were used forquantification. Plots of % loss versus time were used to estimate T50values, being the time taken for first 50% loss of test compound.

Solubility

Saturated solutions of test compounds were prepared in either aqueousbuffer solutions (10 mM mixed phosphate, pH 7.20) or in heptane.Typically 1 mg of test compound in a 2 dram vial with 1 mL of buffer orheptane was left overnight (hours) on a roller shaker after an initialminute period in a sonic bath. Saturated samples were then filteredthrough Millex-HV 0.45 micron syringe driven filters (aqueous ornon-aqueous version dependent on solvent). Aqueous samples were thenanalysed by direct injection on LCMS, and peak areas using PDA detectionwere compared with standards of known concentration; heptane sampleswere first dried and redissolved in an LC compatible solvent, typically30:70 acetonitrile: 0.2% formic acid. Protocol variations includedpre-saturation of the filters for compounds expected to have very lowsolubility, and centrifugation of the saturated samples for oils.

Table 3 below illustrates surprising physical chemistry properties(partition coefficient LogP, Solubility in heptane and/orphotostability) with respect to the prior art compounds of WO2017/207362.

TABLE 3 Solubility in Solubility in Photo- water heptane stability No.Compound Name Structure LogP (ppm) (ppm) T₅₀ (h) E-0 2-[(2,6-difluoro-4-pyridyl)amino]-N- (2,2-dimethyl cyclobutyl)-5-methyl- thiazole-4-carboxamide

5.08 0.70 4.1 3.5 I.b.607 methyl 3-[(2,6- difluoro-4-pyridyl)-[4-[(2,2-dimethyl cyclobutyl)carbamoyl]- 5-methyl-thiazol-2-yl]amino]-3-oxo- propanoate

3.59 12 224 4.4 I.b.614 2-[(2,6-difluoro-4- pyridyl)-(furan-2-carbonyl)amino]-N- (2,2-dimethyl cyclobutyl)-5-methyl- thiazole-4-carboxamide

4.61 0.054 98 14 I.b.616 phenyl N-(2,6- difluoro-4-pyridyl)-N-[4-[(2,2-dimethyl cyclobutyl)carbamoyl]- 5-methyl-thiazol-2-yl]carbamate

5.34 0.10 673 18 I.b.600 2-[(2,6-difluoro-4- pyridyl)-(2-methoxyacetyl)amino]-N- (2,2- dimethylcyclobutyl)- 5-methyl-thiazole-4-carboxamide

3.35 18 859 2.8 I.b.599 ethyl N-(2,6-difluoro- 4-pyridyl)-N-[4-[(2,2-dimethylcyclobutyl) carbamoyl]-5-methyl- thiazol-2-yl] carbamate

4.58 1.0 >1300 11 I.b.598 methyl N-(2,6- difluoro-4-pyridyl)-N-[4-[(2,2-dimethyl cyclobutyl)carbamoyl]- 5-methyl-thiazol-2-yl]carbamate

4.21 1.4 1155 6.2 I.b.595 2-[(2,6-difluoro-4- pyridyl)-formyl-amino]-N-(2,2- dimethylcyclobutyl)- 5-methyl-thiazole-4- carboxamide

3.61 2.5 193 2.8 I.b.612 ethyl 2-[(2,6-difluoro- 4-pyridyl)-[4-[(2,2-dimethylcyclobutyl) carbamoyl]-5-methyl- thiazol-2-yl]amino]-2-oxo-acetate

4.34 nd 379 5.5 I.b.596 2-[acetyl-(2,6- difluoro-4-pyridyl)amino]-N-(2,2- dimethylcyclobutyl)- 5-methyl-thiazole-4- carboxamide

3.80 3.7 619 5.5

Biological Examples Example B1 Alternaria solani/Tomato/Leaf Disc (EarlyBlight)

Tomato leaf disks cv. Baby are placed on agar in multiwell plates(24-well format) and sprayed with the formulated test compound dilutedin water. The leaf disks are inoculated with a spore suspension of thefungus 2 days after application. The inoculated leaf disks are incubatedat 23° C./21° C. (day/night) and 80% rh under a light regime of 12/12 h(light/dark) in a climate cabinet and the activity of a compound isassessed as percent disease control compared to untreated when anappropriate level of disease damage appears on untreated check disk leafdisks (- 7 days after application).

The following compounds gave at least 80% control of Alternaria solaniat 200 ppm when compared to untreated control under the same conditions,which showed extensive disease development: I.b.595, I.b.596, I.b.600,I.b.603, I.b.604, I.b.606, I.b.607, I.b.608, I.b.612, I.b.613, I.b.617,I.b.815, I.b.816, I.b.817, I.b.818, I.c.812, I.c.813.

Example B2 Botryotinia fuckeliana (Botrytis cinerea)/Liquid Culture(Gray Mould)

Conidia of the fungus from cryogenic storage are directly mixed intonutrient broth (Vogels broth). After placing a (DMSO) solution of testcompound into a microtiter plate (96-well format), the nutrient brothcontaining the fungal spores is added. The test plates are incubated at24° C. and the inhibition of growth is determined photometrically 3-4days after application.

The following compounds gave at least 80% control of Botryotiniafuckeliana at ppm when compared to untreated control under the sameconditions, which showed extensive disease development: I.b.595,I.b.596, I.b.600, I.b.612, I.b.613, I.b.815, I.b.818.

Example B3 Glomerella lagenarium (Colletotrichum lagenarium)/liquidculture (Anthracnose)

Conidia of the fungus from cryogenic storage are directly mixed intonutrient broth (PDB potato dextrose broth). After placing a (DMSO)solution of test compound into a microtiter plate (96-well format), thenutrient broth containing the fungal spores is added. The test platesare incubated at 24° C. and the inhibition of growth is measuredphotometrically 3-4 days after application. The following compounds gaveat least 80% control of Glomerella lagenarium at ppm when compared tountreated control under the same conditions, which showed extensivedisease development: I.b.595, I.b.596, I.b.600, I.b.603, I.b.604,I.b.606, I.b.607, I.b.608, I.b.612, I.b.613, I.b.815, I.b.816, I.b.817,I.b.818, I.b.820, I.c.600, I.c.811, I.c.812, I.c.813, I.c.814.

Example B4 Blumeria graminis f. sp. tritici (Erysiphe graminis f. sp.tritici)/wheat/leaf disc preventative (Powdery mildew on wheat)

Wheat leaf segments cv. Kanzler are placed on agar in a multiwell plate(24-well format) and sprayed with the formulated test compound dilutedin water. The leaf disks are inoculated by shaking powdery mildewinfected plants above the test plates 1 day after application. Theinoculated leaf disks are incubated at ° C. and 60% rh under a lightregime of 24 h darkness followed by 12 h light/12 h darkness in aclimate chamber and the activity of a compound is assessed as percentdisease control compared to untreated when an appropriate level ofdisease damage appears on untreated check leaf segments (6-8 days afterapplication).

The following compounds gave at least 80% control of Blumeria graminisf. sp. tritici at 200 ppm when compared to untreated control under thesame conditions, which showed extensive disease development: I.a.596,I.a.600, I.a.601, I.a.812, I.b.595, I.b.596, I.b.598, I.b.599, I.b.600,I.b.603, I.b.604, I.b.606, I.b.607, I.b.608, I.b.610, I.b.612, I.b.613,I.b.614, I.b.615, I.b.616, I.b.617, I.b.618, I.b.815, I.b.816, I.b.817,I.b.818, I.b.820, I.c.596, I.c.600, I.c.811, I.c.812, I.c.813, I.c.814.

Example B5 Fusarium culmorum/wheat/spikelet preventative (Head blight)

Wheat spikelets cv. Monsun are placed on agar in multiwell plates(24-well format) and sprayed with the formulated test compound dilutedin water. The spikelets are inoculated with a spore suspension of thefungus 1 day after application. The inoculated spikelets are incubatedat ° C. and 60% rh under a light regime of 72 h semi darkness followedby 12 h light/12 h darkness in a climate chamber and the activity of acompound is assessed as percent disease control compared to untreatedwhen an appropriate level of disease damage appears on untreated checkspikelets (6-8 days after application). The following compounds gave atleast 80% control of Fusarium culmorum at 200 ppm when compared tountreated control under the same conditions, which showed extensivedisease development: I.b.600.

Example B6 Gibberella zeae (Fusarium graminearum)/wheat/spikeletpreventative (Head blight)

Wheat spikelets cv. Monsun are placed on agar in multiwell plates(24-well format) and sprayed with the formulated test compound dilutedin water. One day after application, the spikelets are inoculated with aspore suspension of the fungus. The inoculated test leaf disks areincubated at ° C. and 60% rh under a light regime of 72 h semi darknessfollowed by 12 h light/12 h darkness in a climate chamber, the activityof a compound is assessed as percent disease control compared tountreated when an appropriate level of disease damage appears onuntreated check spikelets (6-8 days after application). The followingcompounds gave at least 80% control of Gibberella zeae at 200 ppm whencompared to untreated control under the same conditions, which showedextensive disease development: I.b.607.

Example B7 Phaeosphaeria nodorum (Septoria nodorum)/wheat/leaf discpreventative (Glume blotch)

Wheat leaf segments cv. Kanzler are placed on agar in a multiwell plate(24-well format) and sprayed with the formulated test compound dilutedin water. The leaf disks are inoculated with a spore suspension of thefungus 2 days after application. The inoculated test leaf disks areincubated at ° C. and 75% rh under a light regime of 12 h light/12 hdarkness in a climate cabinet and the activity of a compound is assessedas percent disease control compared to untreated when an appropriatelevel of disease damage appears in untreated check leaf disks (−7 daysafter application).

The following compounds gave at least 80% control of Phaeosphaerianodorum at 200 ppm when compared to untreated control under the sameconditions, which showed extensive disease development: I.b.603,I.b.604, I.b.607, I.a.812.

Example B8 Monographella nivalis (Microdochium nivale)/liquid culture(foot rot cereals)

Conidia of the fungus from cryogenic storage are directly mixed intonutrient broth (PDB potato dextrose broth). After placing a (DMSO)solution of test compound into a microtiter plate (96-well format), thenutrient broth containing the fungal spores is added. The test platesare incubated at 24° C. and the inhibition of growth is determinedphotometrically 4-days after application. The following compounds gaveat least 80% control of Monographella nivalis at ppm when compared tountreated control under the same conditions, which showed extensivedisease development: I.a.600, I.b.595, I.b.596, I.b.600, I.b.603,I.b.604, I.b.606, I.b.607, I.b.608, I.b.612, I.b.613, I.b.615, I.b.616,15 I.b.817, I.b.618, I.b.815, I.b.816, I.b.818, I.b.820, I.c.600,I.c.811, I.c.812, I.c.813, I.c.814.

Example B9 Mycosphaerella arachidis (Cercospora arachidicola)/liquidculture (early leaf spot)

Conidia of the fungus from cryogenic storage are directly mixed intonutrient broth (PDB potato dextrose broth). After placing a (DMSO)solution of test compound into a microtiter plate (96-well format), thenutrient broth containing the fungal spores is added. The test platesare incubated at 24° C. and the inhibition of growth is determinedphotometrically 4-days after application.

The following compounds gave at least 80% control of Mycosphaerellaarachidis at ppm when compared to untreated control under the sameconditions, which showed extensive disease development: I.b.595,I.b.600, I.b.603, I.b.604, I.b.606, I.b.607, I.b.612, I.b.816, I.c.812.

Example B10 Phakopsora pachyrhizi/soybean/preventative (soybean rust)

Soybean leaf disks are placed on water agar in multiwell plates (24-wellformat) and sprayed with the formulated test compound diluted in water.One day after application leaf discs are inoculated by spraying a sporesuspension on the lower leaf surface. After an incubation period in aclimate cabinet of 24-36 hours in darkness at ° C. and 75% rh leaf discare kept at ° C. with 12 h light/day and 75% rh. The activity of acompound is assessed as percent disease control compared to untreatedwhen an appropriate level of disease damage appears in untreated checkleaf disks (12-14 days after application).

The following compounds gave at least 80% control of Phakopsorapachyrhizi at 200 ppm when compared to untreated control under the sameconditions, which showed extensive disease development: I.a.601,I.b.595, I.b.600, I.b.603, I.b.604,1.b.612, I.b.613, I.b.815, I.b.816,I.b.818.

Example B11 Plasmopara viticola/grape/leaf disc preventative (lateblight)

Grape vine leaf disks are placed on water agar in multiwell plates(24-well format) and sprayed with the formulated test compound dilutedin water. The leaf disks are inoculated with a spore suspension of thefungus 1 day after application. The inoculated leaf disks are incubatedat 19° C. and 80% rh under a light regime of 12 h light/12 h darkness ina climate cabinet and the activity of a compound is assessed as percentdisease control compared to untreated when an appropriate level ofdisease damage appears in untreated check leaf disks (6-8 days afterapplication). The following compounds gave at least 80% control ofPlasmopara viticola at 200 ppm when compared to untreated control underthe same conditions, which showed extensive disease development:I.b.603, I.b.607.

Example B12: Puccinia recondita f. sp. tritici/wheat/leaf disc curative(Brown rust)

Wheat leaf segments cv. Kanzler are placed on agar in multiwell plates(24-well format). The leaf segments are inoculated with a sporesuspension of the fungus. Plates are stored in darkness at 19° C. and75% rh. The formulated test compound diluted in water is applied 1 dayafter inoculation. The leaf segments are incubated at 19° C. and 75% rhunder a light regime of 12 h light/12 h darkness in a climate cabinetand the activity of a compound is assessed as percent disease controlcompared to untreated when an appropriate level of disease damageappears in untreated check leaf segments (6-8 days after application).

The following compounds gave at least 80% control of Puccinia reconditaf. sp. tritici at 200 ppm when compared to untreated control under thesame conditions, which showed extensive disease development: I.b.595,I.b.600, I.b.603, I.b.604, I.b.606, I.b.607, I.b.608, I.b.612, I.b.618,I.b.815, I.b.816, I.b.818.

Example B13 Puccinia recondita f. sp. tritici/wheat/leaf discpreventative (Brown rust)

Wheat leaf segments cv. Kanzler are placed on agar in multiwell plates(24-well format) and sprayed with the formulated test compound dilutedin water. The leaf disks are inoculated with a spore suspension of thefungus 1 day after application. The inoculated leaf segments areincubated at 19° C. and 75% rh under a light regime of 12 h light/12 hdarkness in a climate cabinet and the activity of a compound is assessedas percent disease control compared to untreated when an appropriatelevel of disease damage appears in untreated check leaf segments (7-9days after application).

The following compounds gave at least 80% control of Puccinia reconditef. sp. tritici at 200 ppm when compared to untreated control under thesame conditions, which showed extensive disease development: I.a.596,I.a.600, I.a.601, I.a.812, I.b.595, I.b.596, I.b.600, I.b.603, I.b.604,I.b.606, I.b.607, I.b.608, I.b.612, I.b.613, I.b.614, I.b.618, I.b.815,I.b.816, I.b.817, I.b.818, I.c.600, I.c.811, I.c.812, I.c.813, I.c.814.

Example B14 Magnaporthe grisea (Pyricularia oryzae)/rice/leaf discpreventative (Rice Blast)

Rice leaf segments cv. Ballila are placed on agar in a multiwell plate(24-well format) and sprayed with the formulated test compound dilutedin water. The leaf segments are inoculated with a spore suspension ofthe fungus 2 days after application. The inoculated leaf segments areincubated at 22° C. and 80% rh under a light regime of 24 h darknessfollowed by 12 h light/12 h darkness in a climate cabinet and theactivity of a compound is assessed as percent disease control comparedto untreated when an appropriate level of disease damage appears inuntreated check leaf segments (- 7 days after application).

The following compounds gave at least 80% control of Magnaporthe griseaat 200 ppm when compared to untreated control under the same conditions,which showed extensive disease development: I.a.596, I.a.600, I.a.601,I.a.812, I.b.595, I.b.596, I.b.598, I.b.600, I.b.603, I.b.604, I.b.606,I.b.607, I.b.608, I.b.612, I.b.613, I.b.614, I.b.615, I.b.616, I.b.617,I.b.618, I.b.815, I.b.816, I.b.817, I.b.818, I.b.820, I.c.596, I.c.596,I.c.600, I.c.811, I.c.812, I.c.813, I.c.814.

Example B15 Pyrenophora teres/barley/leaf disc preventative (Net blotch)

Barley leaf segments cv. Hasso are placed on agar in a multiwell plate(24-well format) and sprayed with the formulated test compound dilutedin water. The leaf segmens are inoculated with a spore suspension of thefungus 2 days after application. The inoculated leaf segments areincubated at ° C. and 65% rh under a light regime of 12 h light/12 hdarkness in a climate cabinet and the activity of a compound is assessedas disease control compared to untreated when an appropriate level ofdisease damage appears in untreated check leaf segments (- 7 days afterapplication).

The following compounds gave at least 80% control of Pyrenophora teresat 200 ppm when compared to untreated control under the same conditions,which showed extensive disease development: I.a.600, I.b.595, I.b.596,I.b.600, I.b.603, I.b.604, I.b.607, I.b.608, I.b.612, I.b.613, I.b.617,I.b.815, I.b.816, I.b.818, I.c.596, I.c.600, I.c.811, I.c.812, I.c.813.

Example B16 Sclerotinia sclerotiorum/liquid culture (cottony rot)

Mycelia fragments of a newly grown liquid culture of the fungus aredirectly mixed into nutrient broth (PDB potato dextrose broth). Afterplacing a (DMSO) solution of test compound into a microtiter plate(96-well format) the nutrient broth containing the fungal material isadded. The test plates are incubated at 24° C. and the inhibition ofgrowth is determined photometrically 3-4 days after application.

The following compounds gave at least 80% control of Sclerotiniasclerotiorum at ppm when compared to untreated control under the sameconditions, which showed extensive disease development: I.b.607,I.b.612.

Example B17 Mycosphaerella graminicola (Septoria tritici)/liquid culture(Septoria blotch)

Conidia of the fungus from cryogenic storage are directly mixed intonutrient broth (PDB potato dextrose broth). After placing a (DMSO)solution of test compound into a microtiter plate (96-well format), thenutrient broth containing the fungal spores is added. The test platesare incubated at 24° C. and the inhibition of growth is determinedphotometrically 4-days after application.

The following compounds gave at least 80% control of Mycosphaerellagraminicola at ppm when compared to untreated control under the sameconditions, which showed extensive disease development: I.b.595,I.b.596, I.b.600, I.b.603, I.b.604, I.b.606, I.b.607, I.b.612, I.b.815,I.b.816, I.b.817, I.b.818, I.c.811, I.c.812, I.c.813, I.c.814.

1. A compound of formula (I):

wherein, Y is C—F, C—H or N; R¹ is hydrogen, C₁-C₆alkyl, C₁-C₆alkoxy,C₁-C₆haloalkyl, C₁-C₆hydroxyalkyl, C₁-C₆alkoxyC₁-C₆alkyl,C₃-C₆cycloalkyl, C₁-C₆alkoxyC₁-C₃alkoxy, C₁-C₆alkoxycarbonyl,C₁-C₆alkoxycarbonylC₁-C₄alkyl, C₁-C₆alkoxycarbonyloxyC₁-C₄alkyl,C₁-C₆alkycarbonyloxyC₁-C₄alkyl, C₂-C₆alkenyloxy, C₂-C₆alkynyloxy,C₁-C₆alkylsulfanyl, di(C₁-C₆alkyl)amino, phenyl, phenylC₁-C₃alkyl,phenylC₁-C₃alkoxyCl-C₃alkyl, phenoxy, or heteroaryl wherein theheteroaryl is a 5- or 6-membered aromatic monocyclic ring comprising 1or 2 heteroatoms individually selected from nitrogen, oxygen and sulfur;R² is hydrogen, halogen, cyano, C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄haloalkyl,or HC(0)NH-; R³ is C₁-C₈alkyl, C₁-Cshaloalkyl, C₁-C₈alkoxy,C₃-C₈cycloalkyl, C₃-C₈cycloalkylC₁-C₂alkyl (wherein the cycloalkylgroups are optionally substituted with 1 to 3 groups represented by R⁴),phenyl, phenylC₁-C₂alkyl, heteroaryl, heteroarylC₁-C₂alkyl, wherein theheteroaryl is a 5- or 6-membered aromatic monocyclic ring comprising 1,2, 3 or 4 heteroatoms individually selected from nitrogen, oxygen andsulfur, heterocyclyl, heterocyclylC₁-C₂alkyl, wherein the heterocyclylis a 4-, 5- or 6-membered non-aromatic monocyclic ring comprising 1, 2or 3 heteroatoms individually selected from nitrogen, oxygen and sulfur,or a 5- to 10-membered non-aromatic spirocyclic carbobi- orcarbotri-cyclyl ring system optionally comprising 1, 2, 3, 4 orheteroatoms individually selected from nitrogen, oxygen and sulfur, andwherein said spirocyclic carbobi- or carbotri-cyclyl ring systems areeach optionally bonded to the rest of the molecule through aC₁-C₂alkylene linker; R⁴ is halogen, C₁-C₄alkyl, C₁-C₄alkoxy, orC₁-C₄haloalkyl; X is N or C—H; or a salt or an N-oxide thereof.
 2. Thecompound according to claim 1, wherein R¹ is hydrogen, C₁-C₄alkyl,C₁-C₄alkoxy, C₁-C₄haloalkyl, C₁-C₄hydroxyalkyl, C₁-C₃alkoxyC₁-C₄alkyl,C₃-C₆cycloalkyl, C₁-C₄alkoxyC₁-C₃alkoxy, C₁-C₃alkoxycarbonyl,C₁-C₃alkoxycarbonylC₁-C₄alkyl, C₁-C₄alkoxycarbonyloxyC₁-C₃alkyl,C₁-C₄alkycarbonyloxyC₁-C₃alkyl, C₃-C₈alkynyloxy, C₁-C₄alkylsulfanyl,di(C₁-C₄alkyl)amino, phenyl, phenylC₁-C₃alkyl,phenylC₁-C₃alkoxyC₁-C₃alkyl, phenoxy, or heteroaryl, wherein theheteroaryl is a 5- or 6-membered aromatic monocyclic ring comprising 1or 2 heteroatoms individually selected from nitrogen, oxygen and sulfur.3. The compound according to claim 1, wherein R¹ is hydrogen,C₁-C₃alkyl, C₁-C₃alkoxy, C₁-C₃haloalkyl, C₁-C₃hydroxyalkyl,methoxyC₁-C₄alkyl, C₃-C₄cycloalkyl, C₁-C₂alkoxyC₁-C₂alkoxy,C₁-C₃alkoxycarbonyl, methoxycarbonylC₁-C₃alkyl,C₁-C₂alkoxycarbonyloxyC₁-C₂alkyl, C₁-C₂alkycarbonyloxyC₁-C₂alkyl,C₃-C₄alkynyloxy, C₁-C₃alkylsulfanyl, diethylamino, phenyl, benzyl,phenoxy, benzyloxyC₁-C₂alkyl, or heteroaryl, wherein the heteroaryl is a5- or 6-membered aromatic monocyclic ring comprising a single heteroatomselected from oxygen and sulfur.
 4. The compound according to claim 1,wherein R¹ is hydrogen, methyl, ethyl, methoxy, ethoxy, fluoromethyl,chloromethyl, bromomethyl, 2,2,2-trifuoroethyl, 1-hydroxyethyl,methoxymethyl, 1-methoxyethyl, 1-ethoxymethyl, 1-methoxy-1-methylethyl,cyclopropyl, methoxyethoxy, ethoxycarbonyl, 2-methoxy-2-oxo-ethyl,2-methoxy-oxo-ethyl, 2-methoxy-oxo-propyl, prop argyl oxy, 1-m ethoxycarb onyl oxy-ethyl, 1-ethoxy carb onyl oxy-ethyl, 1-m ethyl carb onyloxy-ethyl, m ethyl carb onyl oxym ethyl, methylsulfanyl, ethylsulfanyl,isopropylsulfanyl, diethylamino, phenyl, benzyl, phenoxy,benzyloxymethyl, 1-benzyloxyethyl, 2-furanyl, or 2-thiophenyl.
 5. Thecompound according to claim 1, wherein R² is halogen, C₁-C₂alkyl,C₁-C₂alkoxy or HC(O)NH—.
 6. The compound according to claim 1, whereinR² is methyl.
 7. The compound according to claim 1, wherein R³ isC₁-C₄alkyl, C₁-C₃alkoxy, C₃-C₆cycloalkyl, C₃-C₆cycloalkylC₁-C₂alkyl(wherein the cycloalkyl groups are optionally substituted with 1 to 3groups represented by R⁴), phenyl, heteroaryl wherein the heteroaryl isa 5- or 6-membered aromatic monocyclic ring comprising 1, 2 or 3heteroatoms individually selected from nitrogen, oxygen and sulfur,heterocyclyl wherein the heterocyclyl is a 4-, 5- or 6-memberednon-aromatic monocyclic ring comprising 1, 2 or 3 heteroatomsindividually selected from nitrogen, oxygen and sulfur, or a 5- to12-membered non-aromatic spirocyclic carbobi- or carbotri-cyclyl ringsystem optionally comprising a single heteroatom selected from nitrogen,oxygen and sulfur.
 8. The compound according to claim 1, wherein R³ isC₃-C₄cycloalkyl, wherein the cycloalkyl groups are optionallysubstituted with 1 or 2 groups represented by R⁴, or R³ is a 6- to8-membered non-aromatic spirocyclic carbobi-cyclyl ring system.
 9. Thecompound according to claim 1, wherein X is N.
 10. The compoundaccording to claim 1, wherein Y is C—F.
 11. The compound according toclaim 1, wherein R³ is cyclobutyl, 2,2-dimethylcyclobutyl orspiro[3.4]octanyl.
 12. An agrochemical composition comprising afungicidally effective amount of a compound of formula (I) according toclaim
 1. 13. The composition according to claim 12, further comprisingat least one additional active ingredient and/or anagrochemically-acceptable diluent or carrier.
 14. A method ofcontrolling or preventing infestation of useful plants byphytopathogenic microorganisms, a fungicidally effective amount of acompound of formula (I) according to claim 1 to the plants, to partsthereof or the locus thereof.
 15. Use of a compound of formula (I)according to claim 1 as a fungicide.